CN105315794A

CN105315794A - Ink set

Info

Publication number: CN105315794A
Application number: CN201510438298.9A
Authority: CN
Inventors: 大堀宽美; 寺本龙亮; 三宅悠帆
Original assignee: Seiko Epson Corp
Current assignee: Seiko Epson Corp
Priority date: 2014-07-24
Filing date: 2015-07-23
Publication date: 2016-02-10
Anticipated expiration: 2035-07-23
Also published as: JP2016029148A; CN105315794B; US20160032125A1; EP2977414A1; US10047234B2; JP6520452B2

Abstract

The invention aims to provide an ink set which has excellent bleeding resistance, initial filling performance and continuous printing performance apart from ozone resistance, light resistance and humidity resistance. There is provided an ink set including at least: a yellow ink; a magenta ink; and a cyan ink, in which the yellow ink includes one or more kinds selected from a group consisting of coloring materials represented by the following Formulae (Y-1) and (Y-2), the magenta ink includes one or more kinds selected from a group consisting of coloring materials represented by the following Formulae (M-1) and (M-2), and the cyan ink includes one or more kinds selected from a group consisting of coloring materials represented by the following Formulae (C-1) and (C-2).

Description

Ink group

Technical field

The present invention relates to ink group.

Background technology

Ink jet recording method with the image of fairly simple device record fine, can obtain and develops rapidly in every respect.Wherein, various research has been carried out to ejection stability etc.Such as, in patent documentation 1, to provide the ink group that can record the good image of ozone resistance, photostabilization and wet fastness on the recording medium as object, disclose the ink group of Yellow ink, magenta ink and the cyan ink possessed containing regulation tinting material.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2008-81693 publication

Summary of the invention

Ink group is filled in the various ink host bodies such as box, bag, Large Copacity tank and uses.Like this, along with the expansion of the use of ink, wish except ozone resistance as described above, photostabilization, wet fastness and bleeding resistance, the ink group that high reliability (initial fillibility, print stability continuously) is also excellent.

The present invention, in order to solve completing at least partially of above-mentioned problem, its object is to provide except ozone resistance, photostabilization and wet fastness, the ink group that bleeding resistance, initial fillibility, continuous printing are also excellent.

The present inventor etc. conduct in-depth research to solve above-mentioned problem.Its result, as long as find that the ink group of the ink possessed containing regulation colorant just can solve above-mentioned problem, thus completes the present invention.

That is, the present invention is as follows.

(1) an ink group, at least possesses Yellow ink, magenta ink and cyan ink,

Above-mentioned Yellow ink contains more than a kind in the colorant being selected from and being represented by following formula (Y-1) and following formula (Y-2),

Above-mentioned magenta ink contains more than a kind in the colorant being selected from and being represented by following formula (M-1) and following formula (M-2),

Above-mentioned cyan ink contains more than a kind in the colorant being selected from and being represented by following formula (C-1) and following formula (C-2).

(in formula (Y-1), R ₄represent substituting group, R ₅expression-OR ₆or-NHR ₇, R ₆and R ₇represent hydrogen atom or substituting group, X ₃represent the linking group of divalent, n0 is 0 or 1, Ar ₃represent the heterocyclic radical of divalent, Ar ₄represent alkyl, aryl or triazinyl.)

(in formula (Y-2), R ₁represent hydrogen atom or substituting group, R ₂represent substituting group, R ₃represent ionic hydrophilic radical or can form the alkyl of ring, n4 is 0 ~ 4, n5 is 2 ~ 5.)

(in formula (M-1), A ^m1the alkylidene group representing the alkylidene group of carbonatoms 1 or 2, the carbonatoms 1 or 2 containing phenylene or the group represented by following formula (M-1-1), X ^m1represent amino, hydroxyl, chlorine atom or the phenoxy group by sulfo group or carboxyl substituted.)

(in formula (M-1-1), R ^m1represent hydrogen atom or alkyl.)

(in above-mentioned formula (M-2), A ^m2represent 5 yuan of heterocyclic radicals,

B ^m21and B ^m22expression-CR respectively ^m21=,-CR ^m22=, or either party represents nitrogen-atoms, the opposing party represents-CR ^m21=or-CR ^m22=,

R ^m23, R ^m24represent hydrogen atom, aliphatic group, aromatic group, heterocyclic radical, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl independently of one another, R ^m23, R ^m24substituting group can be had further,

G ^m2, R ^m21, R ^m22represent hydrogen atom independently of one another, halogen atom, aliphatic group, aromatic group, heterocyclic radical, cyano group, carboxyl, formamyl, alkoxy carbonyl, aryloxycarbonyl, acyl group, hydroxyl, alkoxyl group, aryloxy, silyl oxygen base, acyloxy, carbamoyloxy, heterocyclic oxy group, alkoxyl group carbonyl oxygen base, aryloxy carbonyl oxygen base, by the amino that alkyl or aryl or heterocyclic radical replace, acyl amino, urea groups, sulphamoylamino, alkoxycarbonyl amino, aryloxycarbonylamino, alkyl and arlysulfonylamino, aryloxycarbonylamino, nitro, alkyl and artyl sulfo, alkyl and aryl sulfonyl, alkyl and aryl sulfonyl kia, sulfamyl, sulfo group, or heterocyclethio, G ^m2, R ^m21, R ^m22can be substituted further,

R ^m21with R ^m23or R ^m23with R ^m24can bonding and form 5 ~ 6 rings.)

In formula (C-1),

R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅represent hydrogen atom independently of one another, halogen atom, alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl, heterocyclic radical, cyano group, hydroxyl, nitro, amino, alkylamino, alkoxyl group, aryloxy, amide group, arylamino, urea groups, sulphamoylamino, alkyl sulfenyl, artyl sulfo, alkoxycarbonyl amino, sulfoamido, formamyl, sulfamyl, alkoxy carbonyl, heterocyclic oxy group, azo-group, acyloxy, carbamoyloxy, silyl oxygen base, aryloxycarbonyl, aryloxycarbonylamino, imide, heterocyclethio, phosphoryl, acyl group or ionic hydrophilic radical.These groups can have substituting group further.

Z ₁, Z ₂, Z ₃and Z ₄independently of one another represent replace or without replace alkyl, replacement or without replace cycloalkyl, replacement or without replace thiazolinyl, replacement or without replace aralkyl, replacement or without replace aryl or replace or without replace heterocyclic radical.Wherein, Z ₁, Z ₂, Z ₃and Z ₄in at least 1 there is ionic hydrophilic radical alternatively base.

L, m, n, p, q ₁, q ₂, q ₃and q ₄represent 1 or 2 independently of one another.

M ₁represent hydrogen atom, metallic element, metal oxide, metal hydroxides or metal halide.

Formula (C-2):

In formula (C-2),

R ₁, R ₄, R ₅, R ₈, R ₉, R ₁₂, R ₁₃and R ₁₆represent hydrogen atom independently of one another, halogen atom, alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl, heterocyclic radical, cyano group, hydroxyl, nitro, amino, alkylamino, alkoxyl group, aryloxy, amide group, arylamino, urea groups, sulphamoylamino, alkyl sulfenyl, artyl sulfo, alkoxycarbonyl amino, sulfoamido, formamyl, sulfamyl, alkoxy carbonyl, heterocyclic oxy group, azo-group, acyloxy, carbamoyloxy, silyl oxygen base, aryloxycarbonyl, aryloxycarbonylamino, imide, heterocyclethio, phosphoryl, acyl group or ionic hydrophilic radical.These groups can have substituting group further.

Z ₅, Z ₆, Z ₇and Z ₈independently of one another represent replace or without replace alkyl, replacement or without replace cycloalkyl, replacement or without replace thiazolinyl, replacement or without replace aralkyl, replacement or without replace aryl or replace or without replace heterocyclic radical.Wherein, Z ₅, Z ₆, Z ₇and Z ₈in at least 1 there is ionic hydrophilic radical alternatively base.

T, u, v, w, q ₅, q ₆, q ₇and q ₈represent 1 or 2 independently of one another.

M ₂represent hydrogen atom, metallic element, metal oxide, metal hydroxides or metal halide.

(2) the ink group according to preceding paragraph (1), wherein, the carbonatoms that above-mentioned Yellow ink, above-mentioned magenta ink or above-mentioned cyan ink contain main chain is the oxirane affixture of the alkyne diol of more than 12 and the carbonatoms of main chain is the alkyne diol of more than 10.

(3) the ink group according to preceding paragraph (1) or (2), wherein, above-mentioned Yellow ink, above-mentioned magenta ink or above-mentioned cyan ink contain polyoxyalkylene alkyl.

(4) the ink group according to any one of preceding paragraph (1) ~ (3), wherein, the content of the carbonatoms of the main chain contained in above-mentioned Yellow ink to be the content of the oxirane affixture of the alkyne diol of more than 12 than the carbonatoms of the main chain contained in above-mentioned magenta ink or above-mentioned cyan ink the be oxirane affixture of the alkyne diol of more than 12 is many.

(5) the ink group according to any one of preceding paragraph (1) ~ (4), wherein, the carbonatoms of the main chain contained in above-mentioned Yellow ink, above-mentioned magenta ink or above-mentioned cyan ink is the content of the oxirane affixture of the alkyne diol of more than 12 is 0.1 ~ 1 quality %.

(6) the ink group according to any one of preceding paragraph (1) ~ (5), wherein, the content of the polyoxyalkylene alkyl contained in above-mentioned Yellow ink, above-mentioned magenta ink or above-mentioned cyan ink is 0.1 ~ 0.3 quality %.

(7) the ink group according to any one of preceding paragraph (1) ~ (6), wherein, above-mentioned magenta ink contains the colorant represented by above-mentioned formula (M-1) and above-mentioned formula (M-2).

(8) the ink group according to any one of preceding paragraph (1) ~ (7), wherein, above-mentioned cyan ink contains the colorant represented by above-mentioned formula (C-1) and above-mentioned formula (C-2).

(9) the ink group according to any one of preceding paragraph (1) ~ (8), wherein, above-mentioned Yellow ink contains the colorant represented by above-mentioned formula (Y-1) and above-mentioned formula (Y-2).

(10) the ink group according to any one of preceding paragraph (1) ~ (9), wherein, possesses at least one party in dyestuff black ink and Pigment black color ink further.

(11) the ink group according to any one of preceding paragraph (1) ~ (10), wherein, above-mentioned dyestuff black ink contains at least a kind in the azo-compound or its salt that are selected from and are represented by following formula (Bk-1) and the colorant represented by following formula (Bw-1).

(in formula (Bk-1), R ¹, R ², R ⁵, R ⁶and R ⁷represent hydrogen atom independently of one another, halogen atom, cyano group, hydroxyl, carboxyl, sulfo group, sulfamyl, N-alkyl amino sulfonyl, N-phenylaminosulfonyl group, the alkyl sulphonyl of the carbonatoms 1 ~ 4 that can be optionally substituted by a hydroxyl group, phospho, nitro, acyl group, urea groups, the alkyl (can be replaced by the alkoxyl group of hydroxyl or carbonatoms 1 ~ 4) of carbonatoms 1 ~ 4, (alkyl can by hydroxyl for the alkoxyl group of carbonatoms 1 ~ 4, the alkoxyl group of carbonatoms 1 ~ 4, sulfo group or carboxyl substituted), acyl amino, (phenyl can by halogen atom for alkyl sulfonyl-amino or phenyl sulfonyl amino, alkyl or nitro replace), R ³and R ⁴represent the alkoxyl group (alkyl can by the alkoxyl group of hydroxyl, carbonatoms 1 ~ 4, sulfo group or carboxyl substituted) of the alkyl (can be replaced by the alkoxyl group of hydroxyl or carbonatoms 1 ~ 4) of hydrogen atom, halogen atom, cyano group, carboxyl, sulfo group, nitro, carbonatoms 1 ~ 4, carbonatoms 1 ~ 4, acyl amino, alkyl sulfonyl-amino or phenyl sulfonyl amino (phenyl can be replaced by halogen atom, alkyl or nitro) independently of one another, n represents 0 or 1.)

(in formula (Bw-1), R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷and R ²⁸represent hydrogen atom independently of one another; Halogen atom; Sulfo group; Carboxyl; Sulfamyl; Formamyl; The alkyl of carbonatoms 1 ~ 4; The alkoxyl group of carbonatoms 1 ~ 4; By the alkoxyl group being selected from the carbonatoms 1 ~ 4 that at least a kind of group in hydroxyl, the alkoxyl group of carbonatoms 1 ~ 4, the alkoxyl group of hydroxyl carbon atom number 1 ~ 4, sulfo group and carboxyl replaces of alternatively base; The alkyl-carbonyl-amino of carbonatoms 1 ~ 4; By the alkyl-carbonyl-amino of the carbonatoms 1 ~ 4 of carboxyl substituted; Urea groups; The alkyl urea groups of single carbon atom number 1 ~ 4; The alkyl urea groups of two carbonatomss 1 ~ 4; By the alkyl urea groups being selected from the single carbon atom number 1 ~ 4 that at least a kind of group in hydroxyl, sulfo group and carboxyl replaces of alternatively base; By the alkyl urea groups being selected from two carbonatomss 1 ~ 4 that at least a kind of group in hydroxyl, sulfo group and carboxyl replaces of alternatively base; Benzoyl-amido; Phenyl ring is selected from the benzoyl-amido that at least a kind of group in halogen atom, the alkyl of carbonatoms 1 ~ 4, nitro, sulfo group and carboxyl replaces; BENZENESUFONYLAMINO; Or phenyl ring is selected from the phenyl sulfonyl amino that at least a kind of group in halogen atom, the alkyl of carbonatoms 1 ~ 4, nitro, sulfo group and carboxyl replaces; X represents the crosslinked group of divalent.)

(12) the ink group according to preceding paragraph (10) or (11), wherein, above-mentioned Pigment black color ink contains self-dispersing pigments.

Embodiment

Below, embodiments of the present invention (hereinafter referred to as " present embodiment ") are described in detail, but the present invention is not limited to these, can various distortion be carried out in the scope not departing from its main idea.

(ink group)

The ink group of present embodiment at least possesses Yellow ink, magenta ink and cyan ink, above-mentioned Yellow ink contains more than a kind in the colorant being selected from and being represented by following formula (Y-1) and following formula (Y-2), above-mentioned magenta ink contains more than a kind in the colorant being selected from and being represented by following formula (M-1) and following formula (M-2), and above-mentioned cyan ink contains more than a kind in the colorant being selected from and being represented by following formula (C-1) and following formula (C-2).

(in formula (M-1-1), R ^m1represent hydrogen atom or alkyl.)

R ^m21with R ^m23or R ^m23with R ^m24can bonding and form 5 ~ 6 rings.)

In formula (C-1),

Formula (C-2):

In formula (C-2),

(substituting group group A)

First, substituting group group A, ionic hydrophilic radical are defined.

Alternatively base group A, be not particularly limited, such as, halogen atom can be enumerated as an example, alkyl, aralkyl, thiazolinyl, alkynyl, aryl, heterocyclic radical, cyano group, hydroxyl, nitro, alkoxyl group, aryloxy, silyl oxygen base, heterocyclic oxy group, acyloxy, carbamoyloxy, alkoxyl group carbonyl oxygen base, aryloxy carbonyl oxygen base, amino, acyl amino, amino carbonyl amino, alkoxycarbonyl amino, aryloxycarbonylamino, sulphamoylamino, alkyl or arlysulfonylamino, sulfydryl, alkyl sulfenyl, artyl sulfo, heterocyclethio, sulfamyl, alkyl or aryl sulfonyl kia, alkyl or aryl sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl, formamyl, aryl or heterocycle azo base, imide, phosphino-, phosphinyl, phosphinyl oxygen base, phosphinyl is amino, silyl, sulfoamido, ionic hydrophilic radical.These substituting groups can be substituted further, as further substituting group, can enumerate the group selected from substituting group group A described above.

More specifically, as halogen atom, such as, fluorine atom, chlorine atom, bromine atoms or atomic iodine can be enumerated.

As alkyl, straight chain, side chain, the replacement of ring-type or the alkyl without replacement can be enumerated, comprise cycloalkyl, bicyclic alkyl, also comprise the tricyclic structure etc. that ring structure is many.Alkyl (alkyl such as, in alkoxyl group, alkyl sulfenyl) in the substituting group below illustrated also represents the alkyl of such concept.Specifically, as alkyl, the alkyl of preferred carbonatoms 1 ~ 30, such as, methyl can be enumerated, ethyl, n-propyl, sec.-propyl, the tertiary butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyano ethyl, 2-ethylhexyl etc., as cycloalkyl, the replacement of preferred carbonatoms 3 ~ 30 or the cycloalkyl without replacement, such as, cyclohexyl can be enumerated, cyclopentyl, 4-n-dodecane butylcyclohexyl etc., as bicyclic alkyl, the replacement of preferred carbonatoms 5 ~ 30 or the bicyclic alkyl without replacement, in other words, the univalent perssad of a hydrogen atom is removed from the bicyclic alkane of carbonatoms 5 ~ 30, such as, dicyclo [1 can be enumerated, 2, 2] heptane-2-base, dicyclo [2, 2, 2] octane-3-base etc.

As aralkyl, can enumerate replace or without replace aralkyl, alternatively or without replace aralkyl, preferred carbonatoms is the aralkyl of 7 ~ 30.Such as can enumerate benzyl and 2-styroyl.

As thiazolinyl, straight chain, side chain, the replacement of ring-type or the thiazolinyl without replacement can be enumerated, comprise cycloalkenyl group, bicyclic alkenyl.Specifically, as thiazolinyl, the replacement of preferred carbonatoms 2 ~ 30 or the thiazolinyl without replacement, such as, vinyl can be enumerated, allyl group, isopentene group, geranyl, oil base etc., as cycloalkenyl group, the replacement of preferred carbonatoms 3 ~ 30 or the cycloalkenyl group without replacement, in other words, the univalent perssad of a hydrogen atom is removed from the cycloolefin of carbonatoms 3 ~ 30, such as, 2-cyclopentenes-1-base can be enumerated, 2-tetrahydrobenzene-1-base etc., as bicyclic alkenyl, replacement or the bicyclic alkenyl without replacement can be enumerated, the replacement of preferred carbonatoms 5 ~ 30 or the bicyclic alkenyl without replacement, in other words, the univalent perssad of a hydrogen atom is removed from the bicyclic alkane with a double bond, such as, dicyclo [2 can be enumerated, 2, 1] hept-2-ene"-1-base, dicyclo [2, 2, 2] oct-2-ene-4-base etc.

As alkynyl, the replacement of preferred carbonatoms 2 ~ 30 or the alkynyl without replacement, such as, can enumerate ethynyl, propargyl, trimethylsilylacetylenyl etc.

As aryl, the replacement of preferred carbonatoms 6 ~ 30 or the aryl without replacement, such as, can enumerate phenyl, p-methylphenyl, naphthyl, a chloro-phenyl-, adjacent Hexadecanoylamino phenyl etc.

As heterocyclic radical, preferably from the replacement of 5 or 6 yuan or the univalent perssad removing a hydrogen atom without the heterogeneous ring compound of the aromatic series replaced or non-aromatic, more preferably the aromatic heterocyclic radical of 5 or 6 yuan of carbonatoms 3 ~ 30, such as, 2-furyl, 2-thienyl, 2-pyrimidyl, 2-[4-morpholinodithio base etc. can be enumerated.

As alkoxyl group, the replacement of preferred carbonatoms 1 ~ 30 or the alkoxyl group without replacement, such as, can enumerate methoxyl group, oxyethyl group, isopropoxy, tert.-butoxy, n-octyloxy, 2-methoxy ethoxy etc.

As aryloxy, the replacement of preferred carbonatoms 6 ~ 30 or the aryloxy without replacement, such as, can enumerate phenoxy group, 2-methylphenoxy, 4-tertiary butyl phenoxy group, 3-nitro-phenoxy, 2-Tetradecanoylamino phenoxy group etc.

As silyl oxygen base, the replacement of preferred carbonatoms 0 ~ 20 or the silyl oxygen base without replacement, such as, can enumerate trimethyl silyl oxygen base, diphenylmethylsilyl oxygen base etc.

As heterocyclic oxy group, the replacement of preferred carbonatoms 2 ~ 30 or the heterocyclic oxy group without replacement, such as, can enumerate 1-phenyltetrazole-5-oxygen base, 2-THP trtrahydropyranyl oxygen base etc.

As acyloxy, the replacement of preferred methanoyl, carbonatoms 2 ~ 30 or without the replacement of the alkyl carbonyl oxy replaced, carbonatoms 6 ~ 30 or without the aryl-carbonyl oxygen replaced, such as, acetoxyl group, new pentane acyloxy, stearoyl-oxy, benzoyloxy, p-methoxyphenyl carbonyl oxygen base etc. can be enumerated.

As carbamoyloxy, the replacement of preferred carbonatoms 1 ~ 30 or the carbamoyloxy without replacement, such as, N can be enumerated, N-dimethyl carbamoyl oxygen base, N, N-diethylamino methanoyl, morpholinyl carbonyl oxygen base, N, N-di-n-octyl amino carbonyl oxygen base, N-n-octyl carbamoyloxy etc.

As alkoxyl group carbonyl oxygen base, the replacement of preferred carbonatoms 2 ~ 30 or without substituted alkoxy carbonyl oxygen base, such as, can enumerate methoxyl group carbonyl oxygen base, oxyethyl group carbonyl oxygen base, tert.-butoxy carbonyl oxygen base, n-octyloxy carbonyl oxygen base etc.

As aryloxy carbonyl oxygen base, the replacement of preferred carbonatoms 7 ~ 30 or the aryloxy carbonyl oxygen base without replacement, such as, can enumerate phenoxy group carbonyl oxygen base, to methoxyphenoxy carbonyl oxygen base, to n-hexadecane oxygen phenoxyl carbonyl oxygen base etc.

As amino, comprise alkylamino, arylamino, heterocyclic amino group, the replacement of preferred amino, carbonatoms 1 ~ 30 or without the replacement of the alkylamino replaced, carbonatoms 6 ~ 30 or without the anilino replaced, such as, methylamino, dimethylamino, anilino, N-metlyl-phenylamine base, diphenyl amino, triazine radical amido etc. can be enumerated.

As acyl amino; the replacement of preferred Formylamino, carbonatoms 1 ~ 30 or without the replacement of the alkyl-carbonyl-amino replaced, carbonatoms 6 ~ 30 or without the aryl-amino-carbonyl replaced; such as; acetylamino can be enumerated, valeryl is amino, lauroyl is amino, benzoyl-amido, 3; 4,5-tri-n-octyl oxygen base benzylcarbonylamino etc.

As amino carbonyl amino, the replacement of preferred carbonatoms 1 ~ 30 or the amino carbonyl amino without replacement, such as, can enumerate carbamoylamino, N, N-Dimethylaminocarbonyl is amino, N, N-diethylaminocarbonyl is amino, morpholinyl carbonyl is amino.

As alkoxycarbonyl amino, the replacement of preferred carbonatoms 2 ~ 30 or without substituted alkoxy carbonylamino, such as, methyloxycarbonylamino, ethoxycarbonylamino group, tertbutyloxycarbonylamino, Octadecane base oxygen base carbonylamino, N-methyl methoxycarbonylamino etc. can be enumerated.

As aryloxycarbonylamino, the replacement of preferred carbonatoms 7 ~ 30 or the aryloxycarbonylamino without replacement, such as, can enumerate phenoxycarbonylamino, to cHorophenoxycarbonyl amino, a n-octyl oxygen phenoxyl carbonylamino etc.

As sulphamoylamino, the replacement of preferred carbonatoms 0 ~ 30 or the sulphamoylamino without replacement, such as, can enumerate sulphamoylamino, N, N-dimethylaminosulfonylamino, N-n-octyl aminosulfonylamino etc.

As alkyl or arlysulfonylamino; the replacement of preferred carbonatoms 1 ~ 30 or without the replacement of the alkyl sulfonyl-amino replaced, carbonatoms 6 ~ 30 or without the arlysulfonylamino replaced; such as; Methylsulfonylamino, butyl sulfuryl amino, phenyl sulfonyl amino, 2 can be enumerated; 3,5-trichlorophenyl sulfuryl amino, p-methylphenyl sulfuryl amino etc.

As alkyl sulfenyl, the replacement of preferred carbonatoms 1 ~ 30 or the alkyl sulfenyl without replacement, such as, can enumerate methylthio group, ethylmercapto group, n-hexadecyl sulfenyl etc.

As artyl sulfo, the replacement of preferred carbonatoms 6 ~ 30 or the artyl sulfo without replacement, such as, can enumerate thiophenyl, to chlorophenylsulfanyl, meta-methoxy thiophenyl etc.

As heterocyclethio, the replacement of preferred carbonatoms 2 ~ 30 or the heterocyclethio without replacement, such as, can enumerate 2-[4-morpholinodithio base sulfenyl, 1-phenyltetrazole-5-base sulfenyl etc.

As sulfamyl; the replacement of preferred carbonatoms 0 ~ 30 or the sulfamyl without replacement; such as; N-ethylsulfamovl can be enumerated; N-(3-dodecyl oxygen base propyl group) sulfamyl, N, N-DimethylsuIfamoyl, N-acetylsulfamoyl, N-benzoyl sulfamyl, N-(N '-phenylcarbamoyl) sulfamyl etc.

As alkyl or aryl sulfonyl kia; the replacement of preferred carbonatoms 1 ~ 30 or without the replacement of the alkyl sulphinyl replaced, carbonatoms 6 ~ 30 or without the aryl sulfonyl kia replaced; such as, methylsulfinyl, ethylsulfinyl, phenylsufinyl, p-methylphenyl sulfinyl etc. can be enumerated.

As alkyl or aryl sulfonyl; the replacement of preferred carbonatoms 1 ~ 30 or without the replacement of the alkyl sulphonyl replaced, carbonatoms 6 ~ 30 or without the aryl sulfonyl replaced; such as, methyl sulphonyl, ethylsulfonyl, phenyl sulfonyl, p-methylphenyl alkylsulfonyl etc. can be enumerated.

As acyl group; the replacement of preferred formyl radical, carbonatoms 2 ~ 30 or the replacement without the alkyl-carbonyl replaced, carbonatoms 7 ~ 30 or the replacement without the aryl carbonyl replaced, carbonatoms 2 ~ 30 or without replace with the heterocyclecarbonyl of carbon atom and carbonyl bonding; such as, can enumerate ethanoyl, valeryl, 2-chloracetyl, stearyl-, benzoyl, to n-octyl oxygen base phenylcarbonyl group, 2-PYRIDYLCARBONYL, 2-furyl carbonyl etc.

As aryloxycarbonyl, the replacement of preferred carbonatoms 7 ~ 30 or without the aryloxycarbonyl replaced, such as, can enumerate phenyloxycarbonyl, adjacent cHorophenoxycarbonyl, m-nitro oxygen base carbonyl, to tertiary butyl phenyloxycarbonyl etc.

As alkoxy carbonyl, the replacement of preferred carbonatoms 2 ~ 30 or without substituted alkoxy carbonyl, such as, can enumerate methoxycarbonyl, ethoxy carbonyl, tert-butoxycarbonyl, Octadecane base oxygen base carbonyl etc.

As formamyl; the replacement of preferred carbonatoms 1 ~ 30 or the formamyl without replacement; such as; formamyl, N-methylcarbamoyl, N can be enumerated; N-formyl-dimethylamino, N, N-di-n-octyl formamyl, N-(methyl sulphonyl) formamyl etc.

As aryl or heterocycle azo base, the replacement of preferred carbonatoms 6 ~ 30 or without the replacement of the arylazo base replaced, carbonatoms 3 ~ 30 or without the heterocycle azo base replaced, such as, phenylazo, rubigan azo-group, 5-ethylmercapto group-1 can be enumerated, 3,4-thiadiazoles-2-base azo-group etc.

As imide, preferably N-succinimido, N phlhalimide base etc. can be enumerated.

As phosphino-, the replacement of preferred carbonatoms 0 ~ 30 or the phosphino-without replacement, such as, can enumerate dimethyl phosphino-, diphenylphosphino, methylphenoxy phosphino-etc.

As phosphinyl, the replacement of preferred carbonatoms 0 ~ 30 or the phosphinyl without replacement, such as, can enumerate phosphinyl, two octyloxy phosphinyls, diethoxy phosphinyl etc.

As phosphinyl oxygen base, the replacement of preferred carbonatoms 0 ~ 30 or the phosphinyl oxygen base without replacement, such as, can enumerate two phenoxy group phosphinyl oxygen bases, two octyloxy phosphinyl oxygen bases etc.

Amino as phosphinyl, the replacement or amino without the phosphinyl replaced of preferred carbonatoms 0 ~ 30, such as, can enumerate dimethoxyphosphinvl amino, dimethylamino phosphinyl is amino.

As silyl, the replacement of preferred carbonatoms 0 ~ 30 or the silyl without replacement, such as, can enumerate trimethyl silyl, t-butyldimethylsilyl, phenyldimethylsilyl etc.

(ionic hydrophilic radical)

Sulfo group, carboxyl, thiocarboxyl group, sulfino, phosphono, dihydroxyl phosphino-, quaternary ammonium group etc. can be enumerated.Particularly preferably sulfo group, carboxyl.In addition; carboxyl, phosphono and sulfo group can be the states of salt; the example forming the counter cation of salt comprises ammonium ion, alkalimetal ion (such as; lithium ion, sodium ion, potassium ion) and organic cation (such as, tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl- ), preferred lithium salts, sodium salt, sylvite, ammonium salt, more preferably lithium salts or take lithium salts as the mixing salt of principal constituent, most preferably lithium salts.

(Yellow ink)

Yellow ink contains more than a kind in the colorant being selected from and being represented by following formula (Y-1) and following formula (Y-2).Yellow ink is preferably containing the colorant represented by following formula (Y-1) and following formula (Y-2).By containing the colorant represented by following formula (Y-1) and following formula (Y-2), there is the trend of the image obtaining tinting strength, photostabilization and excellent hue.

(colorant represented by formula (Y-1))

Below, the azoic dyestuff (yellow dyes) represented by formula (Y-1) is described.

In formula (Y-1), as by Ar ₃the heterocyclic radical of the divalent represented, preferably 5 yuan or 6 rings, they can form condensed ring further.In addition, can be heteroaromatic, also can be non-aromatic heterocyclic.As by Ar ₃the heterocyclic radical of the divalent represented, such as, can enumerate pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline 99.9, quinazoline, cinnolines, phthalazines, quinoxaline, pyrroles, indoles, furans, cumarone, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole, azoles, benzo azoles, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazoles, different azoles, benzisoxa azoles, tetramethyleneimine, piperidines, piperazine, imidazolidine, thiazoline etc.Wherein optimization aromatic heterocyclic radical, if illustrate its preference in the same manner as before, can enumerate pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazoles, imidazoles, benzoglyoxaline, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazoles.Most preferably thiadiazoles.They can have substituting group, alternatively the example of base, identical with aforesaid substituting group group A.

In formula (Y-1), by R ₄, R ₆and R ₇the substituting group represented is selected from above-mentioned substituting group group A.

In formula (Y-1), R ₄be preferably alkyl, alkoxyl group, aryl, be preferably the alkyl of carbonatoms 1 ~ 4, be more preferably methyl, ethyl, the tertiary butyl, phenyl, methoxyl group, oxyethyl group, more preferably the tertiary butyl.

In formula (Y-1), R ₅be preferably replacement or the amino without replacement, R ₅be more preferably the amino without replacing.

In addition, in formula (Y-1), Ar ₄be preferably replacement or the aryl without replacement, more preferably replacement or the phenyl without replacement.

In formula (Y-1), as R ₄, R ₅, Ar ₄there is substituting group during substituting group further, above-mentioned substituting group group A can be enumerated, preferred alkyl, aryl, heterocyclic radical, cyano group, hydroxyl, nitro or alkoxyl group, further preferred alkyl, aryl or heterocyclic radical.

In formula (Y-1), by X ₃the linking group of the divalence represented is preferably heterocyclic radical (the such as 6-chloro-1 of alkylidene group (such as methylene radical, ethylidene, propylidene, butylidene, pentylidene), alkenylene (such as vinylidene, propenylidene), alkynylene (such as ethynylene, sub-proyl), arylidene (such as phenylene, naphthylidene), divalence, 3,5-triazine-2,4-bis-base, pyrimidine-2,4-bis-base, quinoxaline-2,3-bis-base) ,-O-,-CO-,-NR _a-(R _afor hydrogen atom, alkyl or aryl) ,-S-,-SO ₂-,-SO-or their combination.

In formula (Y-1), by X ₃represent alkylidene group, alkenylene, alkynylene, arylidene, divalence heterocyclic radical, by R _athe alkyl represented or aryl can have substituting group.The alternatively example of base is identical with above-mentioned substituting group.By R _arepresent alkyl and aryl comprise replace or without replace alkyl or aryl.Alternatively or without replace alkyl, preferred carbonatoms is the alkyl of 1 ~ 30, alternatively or without replace aryl, the aryl of preferred carbonatoms 6 ~ 30.

In formula (Y-1), by X ₃in the linking group of the divalence represented, be more preferably the alkylidene group of carbonatoms less than 10, the alkenylene of carbonatoms less than 10, the alkynylene of carbonatoms less than 10, the arylidene of carbonatoms 6 ~ 10, the heterocyclic radical of divalence ,-O-,-S-or their combination, further preferably alkylidene group or-S-or their combination.

The total carbon atom number of the linking group of divalence is preferably 0 ~ 50, is more preferably 0 ~ 30, most preferably is 0 ~ 10.

In formula (Y-1), by Ar ₄the aryl represented or arylidene, with aforesaid by R _aaryl or the arylidene implication of expression are identical, and preferred example is also identical.In addition, by Ar ₄the triazinyl represented can have the substituting group of 1 valency, and (substituting group of 1 valency is identical with aforesaid substituting group group A implication, and preferred example is also identical.)。

As the colorant represented by formula (Y-1), be not particularly limited, such as, the compound preferably represented by following formula (Y-1-1), the compound more preferably represented by following formula (Y-1-2).

(in formula (Y-1-1), R ₄represent substituting group, R ₅expression-OR ₆or-NHR ₇, R ₆and R ₇represent hydrogen atom or substituting group, X ₃represent the linking group of divalent, n0 is 0 or 1, Ar ₃represent the heterocyclic radical of divalent, A ₁represent ionic hydrophilic radical, n1 represents 0 ~ 2.)

In formula (Y-1-1), R ₄, R ₅, Ar ₃, n0 and X ₃with the R in formula (Y-1) ₄, R ₅, Ar ₃, n0 and X ₃implication is identical, and preferred example is also identical.

In formula (Y-1-1), by A ₁the ionic hydrophilic radical represented is-SO preferably ₃m or-CO ₂m, more preferably-SO ₃m, particularly preferably-CO ₂k.M represents the counter cation of hydrogen atom or monovalence independently of one another, as the counter cation of monovalence, such as can enumerate ammonium ion, alkalimetal ion (such as, lithium ion, sodium ion, potassium ion) and organic cation (such as, tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl- ), preferred lithium salts, sodium salt, sylvite, ammonium salt, more preferably sylvite or take sylvite as the mixing salt of principal constituent, most preferably sylvite.

Formula (Y-1-2):

(in formula (Y-1-2), R ₂₀represent the linking group that alkylidene group ,-S-or the combination by them are formed, R ₂₁represent ionic hydrophilic radical, R ₁₁represent alkyl, R ₁₂represent amino.)

In formula (Y-1-2), R ₂₀with formula (Y-1) by X ₃alkylidene group implication in the linking group of the divalence represented is identical, and preferred example is also identical.

In formula (Y-1-2), R ₂₁represent carboxyl (-CO ₂m), M represents the counter cation of hydrogen atom or monovalence independently of one another, as the counter cation of monovalence, such as can enumerate ammonium ion, alkalimetal ion (such as, lithium ion, sodium ion, potassium ion) and organic cation (such as, tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl- ), preferred lithium salts, sodium salt, sylvite, ammonium salt, more preferably sylvite or take sylvite as the mixing salt of principal constituent, most preferably sylvite.

In formula (Y-1-2), by R ₁₁represent alkyl and by R ₁₂the amino represented respectively with the R of above-mentioned formula (Y-1) ₄, R ₅in alkyl identical with amino implication, preferred example is also identical.

The concrete example of the compound represented by formula (Y-1) is below shown, the compound used in present embodiment is not limited to following example.Should illustrate, in concrete example, Et refers to ethyl, and Ph refers to phenyl.

The compound represented by formula (Y-1) can synthesize by general synthesis method, such as can by the diazo component recorded in Japanese Unexamined Patent Publication 2004-083903 publication with coupling components changes, carry out various combination to synthesize.

The content of the colorant represented by formula (Y-1), relative to the total amount of Yellow ink, is preferably 1.0 ~ 7.0 quality %, is more preferably 2.0 ~ 6.0 quality %, more preferably 3.0 ~ 5.0 quality %.By the content of colorant that represented by formula (Y-1) in above-mentioned scope, there is the trend of the image obtaining tinting strength, photostabilization and excellent hue.

(colorant represented by formula (Y-2))

Below, the colorant represented by formula (Y-2) is described.

In formula (Y-2), as by R ₁and R ₂the substituting group represented, can enumerate the alkyl that can be substituted, the alkoxyl group that can be substituted, the aryl that can be substituted, the heterocyclic radical ,-NR that can be substituted independently of one another ⁸r ⁹,-NHCOR ⁸,-NHCONR ⁸r ⁹,-C (O) R ⁸,-C (O) OR ⁸,-C (O) NR ⁸r ⁹,-PO ₃h ₂,-SR ⁸,-SO ₂r ⁸,-SO ₂nR ⁸r ⁹,-SOR ⁸,-SO ₃h ,-CF ₃,-CN ,-NO ₂, hydroxyl or halogen.Here, R ⁸and R ⁹be H, the alkyl of carbonatoms 1 ~ 8 that can be substituted, the aryl (such as phenyl) that can be substituted, the heterocyclic radical that can be substituted independently of one another, or R ⁸and R ⁹the five-ring or six-ring (such as, piperidines, pyrrolidone, pyridine, piperazine (piperizine) or morpholine) that can be substituted can be formed together with the nitrogen-atoms of their institute's bondings.

In formula (Y-2), by R ₃the ionic hydrophilic radical represented is-SO preferably ₃m or-CO ₂m, more preferably-SO ₃m.M represents the counter cation of hydrogen atom or monovalence independently of one another, as the counter cation of monovalence, such as can enumerate ammonium ion, alkalimetal ion (such as, lithium ion, sodium ion, potassium ion) and organic cation (such as, tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl- ), preferred lithium salts, sodium salt, sylvite, ammonium salt.By R ₃the ionic hydrophilic radical represented is preferably sulfo group, the more preferably sylvite of sulfo group.

In formula (Y-2), as by R ₃the alkyl represented, can have substituting group, is preferably the alkyl of carbonatoms 1 ~ 4, can enumerates methyl, ethyl, propyl group, sec.-propyl, butyl, the sec-butyl that can be replaced by hydroxyl, halogen, carboxyl or sulfo group etc.As an example, not circumscribed, but trifluoromethyl, hydroxyethyl, sulfapropyl and carboxy ethyl can be enumerated.

In formula (Y-2), as by R ₃the mutual bonding of alkyl represented and form ring time ring, the aryl that can be substituted or the heterocyclic radical that can be substituted can be enumerated, as this aryl and heterocycle, the aryl in aforesaid substituting group group A and heterocyclic radical can be enumerated, the ring formed as mutual bonding, such as can enumerate phenyl ring, naphthalene nucleus, be preferably phenyl ring.

In addition, by R ₃the mutual bonding of alkyl represented and the ring that formed, preferably replaced by sulfonic group.

In formula (Y-2), R ₁and R ₂for can be substituted alkoxyl group time, the alkoxyl group of the carbonatoms 1 ~ 8 that they preferably can be substituted, more preferably the alkoxyl group of carbonatoms 1 ~ 4, such as, can by the methoxyl group of hydroxyl, halogen or carboxyl substituted, oxyethyl group, propoxy-, isopropoxy, butoxy.As an example, not circumscribed, but carboxypropyl oxygen base, Carboxyethoxy, hydroxyl-oxethyl or chloroethoxy can be enumerated.

In formula (Y-2), R ₁and R ₂for can be substituted aryl time, the phenyl that preferably can be substituted.As the substituting group desired by aryl rings, such as, the alkoxyl group ,-NR of the alkyl of carbonatoms 1 ~ 8, carbonatoms 1 ~ 8 can be enumerated ⁸r ⁹,-NHCOR ⁸,-NHCONR ⁸r ⁹,-C (O) R ⁸,-C (O) OR ⁸,-C (O) NR ⁸r ⁹,-PO ₃h ₂,-SR ⁸,-SO ₂r ⁸,-SO ₂nR ⁸r ⁹,-SOR ⁸,-SO ₃h ,-CF ₃,-CN ,-NO ₂, hydroxyl or halogen, here, R ⁸and R ⁹described in before.As an example, not circumscribed, can enumerate carboxyl phenyl, sulfophenyl, nitrophenyl and chloro-phenyl-.

In formula (Y-2), R ₁and R ₂for can be substituted heterocyclic radical time, any one in the aliphatic heterocyclyl radical that they preferably can be substituted or the aromatic heterocycle that can be substituted, such as, thiophene, pyrazoles, triazole, thiadiazoles, thiazole, imidazoles, pyridine, pyrrolidone, piperazine, morpholine or pyrimidine for being substituted.As the substituting group desired by heterocycle, such as, the alkyl ,-NR of carbonatoms 1 ~ 8 can be enumerated ⁸r ⁹,-NHCOR ⁸,-NHCONR ⁸r ⁹,-C (O) OR ⁸,-C (O) NR ⁸r ⁹,-SR ⁸,-SO ₂r ⁸,-SO ₂nR ⁸r ⁹,-SOR ⁸,-SO ₃h ,-CF ₃,-CN ,-NO ₂, hydroxyl or halogen, here, R ⁸and R ⁹described in before.As an example, not circumscribed, but carboxyl triazole, chloropyridine base and cyano thiophene can be enumerated.

In formula (Y-2), R ₁and R ₂be hydrogen atom, hydroxyl, the alkyl (preferable methyl or ethyl) of carbonatoms 1 ~ 4 that can be substituted, alkoxyl group (preferred methoxyl group or oxyethyl group) ,-NR of carbonatoms 1 ~ 4 that can be substituted independently of one another ⁸r ⁹-SO ₂nR ⁸r ⁹or-NHCONR ⁸r ⁹, here, R ⁸and R ⁹as above, more preferably R ⁸for H, R ⁹for H, the alkyl (preferable methyl or ethyl) of carbonatoms 1 ~ 4 that can be substituted or aryl (preferred phenyl).

In formula (Y-2), R ₁and R ₂be preferably hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4, the alkoxyl group of carbonatoms 1 ~ 4, carboxylic acid group ,-NR independently of one another ⁸r ⁹or NHCONH ₂.

In formula (Y-2), R ₁be more preferably hydroxyl or-NR ⁸r ⁹.Preferred R ⁸for H, R ⁹for H, the alkyl (preferable methyl or ethyl) of carbonatoms 1 ~ 4 that can be substituted, more preferably R ⁸for H, R ⁹for the alkyl (preferable methyl or ethyl) of carbonatoms 1 ~ 4 be optionally substituted by a hydroxyl group.

In formula (Y-2), R ₂be more preferably hydrogen atom, the alkyl of carbonatoms 1 ~ 4 or carboxylic acid, because have solubleness good especially, light fastness and resistance to ozone fastness, so more preferably carboxylic acid.

In formula (Y-2), n4 is 0 ~ 4, is preferably 1 ~ 4, is more preferably 1 ~ 2.

In formula (Y-2), n5 is 2 ~ 5, is preferably 2 ~ 4, is more preferably 2 ~ 4, more preferably 2 ~ 3.This is because the solubleness of compound in water-based liquid medium of formula (Y-2) improves.

As the colorant represented by formula (Y-2), be not particularly limited, such as, the compound preferably represented by following formula (Y-2-1) or the compound represented by following formula (Y-2-2).

(in formula (Y-2-1), R ₁represent hydrogen atom or substituting group, R ₂represent substituting group, A ₂represent ionic hydrophilic radical, n4 is that 0 ~ 4, n2 represents 2 ~ 4.)

In formula (Y-2-1), by A ₂the ionic hydrophilic radical represented, preferably-SO ₃m or-CO ₂m, more preferably-SO ₃m.M represents the counter cation of hydrogen atom or monovalence independently of one another, as the counter cation of monovalence, such as can enumerate ammonium ion, alkalimetal ion (such as, lithium ion, sodium ion, potassium ion) and organic cation (such as, tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl- ), preferred lithium salts, sodium salt, sylvite, ammonium salt.By A ₂the ionic hydrophilic radical represented is preferably sulfo group, the more preferably sylvite of sulfo group.

In formula (Y-2-1), R ₁and R ₂with the R in formula (Y-2) ₁and R ₂implication is identical, and preferred example is also identical.

In formula (Y-2-1), n4 is 0 ~ 4, is preferably 1 ~ 4, is more preferably 1 ~ 2.N2 is preferably 2 ~ 4, is more preferably 2 ~ 4, and more preferably 2 ~ 3.This is because the solubleness of compound in water-based liquid medium of formula (Y-2-1) improves.

(in formula (Y-2-2), R ₁represent hydrogen atom or substituting group, R ₂represent substituting group, A ₃represent ionic hydrophilic radical, n4 is that 0 ~ 4, n3 represents 2 ~ 4.)

In formula (Y-2-2), by A ₃the ionic hydrophilic radical represented is-SO preferably ₃m or-CO ₂m, more preferably-SO ₃m.M represents the counter cation of hydrogen atom or monovalence independently of one another, as the counter cation of monovalence, such as can enumerate ammonium ion, alkalimetal ion (such as, lithium ion, sodium ion, potassium ion) and organic cation (such as, tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl- ), preferred lithium salts, sodium salt, sylvite, ammonium salt.By A ₃the ionic hydrophilic radical represented is preferably sulfo group, the more preferably sylvite of sulfo group.

In formula (Y-2-2), R ₁and R ₂with the R in formula (Y-2) ₁and R ₂implication is identical, and preferred example is also identical.

In formula (Y-2-2), n4 is 0 ~ 4, is preferably 1 ~ 4, is more preferably 1 ~ 2.

In formula (Y-2-2), n3 is preferably 2 ~ 4, is more preferably 2 ~ 4, and more preferably 2 ~ 3.This is because the solubleness of compound in water-based liquid medium of formula (Y-2-2) improves.

The compound that the compound represented by formula (Y-2-2) is more preferably represented by following formula (Y-2-3).

(in formula (Y-2-3), R ₈represent hydroxyl or-NR ⁸r ⁹, R ₉represent the alkyl of hydrogen atom, hydroxyl, carbonatoms 1 ~ 4, the alkoxyl group of carbonatoms 1 ~ 4, carboxylic acid group ,-NR independently of one another ⁸r ⁹or NHCONH ₂, R ⁸and R ⁹be H, the alkyl of carbonatoms 1 ~ 8 that can be substituted, the aryl (such as phenyl) that can be substituted, the heterocyclic radical that can be substituted independently of one another, or R ⁸and R ⁹the five-ring or six-ring that can be substituted can be formed, R together with the nitrogen-atoms of their institute's bondings ₁₀represent carboxyl or sulfo group independently of one another.)

In formula (Y-2-3), as R ⁸and R ⁹the five-ring formed or six-ring, such as, can enumerate piperidines, pyrrolidone, pyridine, piperazine (piperizine) or morpholine.They can have substituting group, alternatively the example of base, can enumerate above-mentioned group of A.By R ₈represent amino, by R ₉the alkyl represented, alkoxyl group, sulfo group, amino carbonyl amino and by R ₁₀the sulfo group and the amino in aforesaid group of A that represent, alkyl, alkoxyl group, sulfo group, amino carbonyl amino, sulfo group implication are identical, and preferred example is also identical.

In formula (Y-2-3), R ¹⁰be preferably sulfo group, the more preferably sylvite of sulfo group.

The compound represented by formula (Y-2) ~ (Y-2-3) can be symmetrical or asymmetrical.Then, the following concrete example that the colorant represented by above-mentioned formula (Y-2) of present embodiment is shown.

The colorant represented by formula (Y-2) can synthesize by general synthesis method, such as can by changing the diazo component recorded in Japanese Unexamined Patent Application Publication 2008-537756 publication and coupling components, carry out various combination to synthesize.

The content of the colorant represented by formula (Y-2), relative to the total amount of Yellow ink, is preferably 1.0 ~ 7.0 quality %, is more preferably 2.0 ~ 6.0 quality %, more preferably 3.0 ~ 5.0 quality %.By the content of colorant that represented by formula (Y-2) in above-mentioned scope, there is the trend of the image obtaining tinting strength, photostabilization and excellent hue.

(magenta ink)

Magenta ink contains more than a kind in the colorant being selected from and being represented by following formula (M-1) and following formula (M-2).Magenta ink is preferably containing the colorant represented by following formula (M-1) and following formula (M-2).By containing the colorant represented by following formula (M-1) and following formula (M-2), there is the trend of the image obtaining color emissivity and excellent moisture resistance.

(colorant represented by formula (M-1))

Below, the colorant represented by formula (M-1) is described in detail.The colorant represented by formula (M-1) can form salt.

(in formula (M-1-1), R ^m1represent hydrogen atom or alkyl.)

In above-mentioned formula (M-1), A ^m1be preferably the alkylidene group of carbonatoms 1 or 2, be more preferably the alkylidene group of carbonatoms 2.

In formula (M-1), X ^m1represent amino, hydroxyl, chlorine atom or the phenoxy group by sulfo group or carboxyl substituted.Wherein, preferably by the phenoxy group of sulfo group or carboxyl substituted, more preferably by the phenoxy group of carboxyl substituted.Possessed the improvement effect of good wet fastness by the phenoxy group of carboxyl substituted, by the phenoxy group of 2 carboxyl substituted, be there is better wet fastness and particularly preferably.

In formula (M-1), as by the concrete example of the phenoxy group of sulfo group or carboxyl substituted, for 4-sulfophenoxy, 2,4-disulfo phenoxy group, 4-carboxyphenoxy, 3,5-di carboxyl phenyloxy, is more preferably 4-carboxyphenoxy, 3,5-di carboxyl phenyloxies, more preferably 3,5-di carboxyl phenyloxies.

As the salt of the compound represented by formula (M-1), ammonium salt or an alkali metal salt can be enumerated.

The content of the colorant represented by formula (M-1), relative to the total amount of magenta ink, is preferably 0.5 quality % ~ 10 quality %, is more preferably 1.0 ~ 9.0 quality %, more preferably 3.0 ~ 8.0 quality %.By the content of colorant that represented by formula (M-1) in above-mentioned scope, there is the trend of the image obtaining color emissivity and excellent moisture resistance.

(colorant represented by formula (M-2))

Below, the colorant represented by formula (M-2) is described in detail.The colorant represented by formula (M-2) can form salt.

R ^m21with R ^m23or R ^m23with R ^m24can bonding and form 5 ~ 6 rings.)

In formula (M-2), as 5 yuan of heterocyclic radicals, such as, pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazoles basic ring, benzothiazole ring, benzo can be enumerated azoles ring, benzisothiazole ring, each heterocyclic radical can also have substituting group.In addition, preferred pyrazole ring in heterocycle.

In formula (M-2), R ^m21in, preferred hydrogen atom or alkyl, more preferably hydrogen atom.

In formula (M-2), R ^m22in, preferred aliphat group, more preferably methyl, ethyl, can branching propyl group or can the butyl of branching.

In formula (M-2), R ^m23, R ^m24represent hydrogen atom, aliphatic group, aromatic group, heterocyclic radical, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl independently of one another.R ^m23, R ^m24substituting group can be had further.

In formula (M-2), R ^m23in, optimization aromatic group, specifically, can enumerate phenyl ring base or naphthalene nucleus base.Above-mentioned R ^m24in, preferred heterocyclic radical, specifically, can enumerate benzothiazole cyclic group.

In formula (M-2), G ^m2, R ^m21, R ^m22represent hydrogen atom independently of one another, halogen atom, aliphatic group, aromatic group, heterocyclic radical, cyano group, carboxyl, formamyl, alkoxy carbonyl, aryloxycarbonyl, acyl group, hydroxyl, alkoxyl group, aryloxy, silyl oxygen base, acyloxy, carbamoyloxy, heterocyclic oxy group, alkoxyl group carbonyl oxygen base, aryloxy carbonyl oxygen base, by the amino that alkyl or aryl or heterocyclic radical replace, acyl amino, urea groups, sulphamoylamino, alkoxycarbonyl amino, aryloxycarbonylamino, alkyl and arlysulfonylamino, aryloxycarbonylamino, nitro, alkyl and artyl sulfo, alkyl and aryl sulfonyl, alkyl and aryl sulfonyl kia, sulfamyl, sulfo group, or heterocyclethio.R ^m23, R ^m24can be substituted further.In addition, R ^m21with R ^m23or R ^m23with R ^m24can bonding and form 5 ~ 6 rings.

In the colorant represented by formula (M-2), the compound preferably represented by following formula (M-21).

(in formula (M-21), R ^m25, R ^m26, R ^m27, R ^m28, R ^m29represent hydrogen atom, alkyl, sulfo group or its salt.In formula (M-21), R ^m25, R ^m29when being alkyl, what form the carbonatoms of this alkyl adds up to more than 3, and they can have substituting group.X ^m2represent hydrogen atom, aliphatic group, aromatic group or heterocyclic radical, Y ^m2and Z ^m2represent hydrogen atom, aliphatic group, aromatic group, heterocyclic radical, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl independently of one another.Each group can have substituting group further.In addition, R ^m25~ R ^m29-SO can be become containing during sulfo group ₃the form of M.At this moment, as M, preferred as alkali atom, at least a kind more preferably in Li and Na.)

In formula (M-21), X ^m2in, particularly preferably aromatic group, ester ring type group, heterocyclic radical, as concrete example, such as can enumerate phenyl ring, pentamethylene ring, cyclohexane ring, suberane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzoglyoxaline ring, azoles ring, benzo azoles ring, thiazole ring, benzothiazole ring, alkane ring, tetramethylene sulfone ring and sulfuration pentamethylene ring etc.Wherein, more preferably heterocycle.

In formula (M-21), Y ^m2and Z ^m2preferred concrete example and dyestuff (M-2) in R ^m23and R ^m24preferred concrete example identical.

In the compound represented by formula (M-21), because there is excellent color emissivity and ozone resistance, so the compound particularly preferably represented by following formula (M-22).

(in formula (M-22), R ^m25, R ^m26, R ^m27, R ^m28, R ^m29, R ^m210, R ^m211, R ^m212, R ^m213, R ^m214represent hydrogen atom, alkyl, sulfo group or its salt, M ^m2represent hydrogen atom or alkali metal atom.In addition, R ^m25and R ^m29when being alkyl, what form the carbonatoms of its alkyl adds up to more than 3, and they can have substituting group further, R ^m210and R ^m214when being alkyl, what form the carbonatoms of this alkyl adds up to more than 3, and they can have substituting group further.)

The content of the colorant represented by formula (M-2), relative to the total amount of magenta ink, is preferably 0.5 quality % ~ 10 quality %, is more preferably 1.0 ~ 9.0 quality %, more preferably 3.0 ~ 8.0 quality %.By the content of colorant that represented by formula (M-2) in above-mentioned scope, there is the trend of the image obtaining color emissivity and excellent moisture resistance.

In addition, in magenta ink, by the colorant represented by formula (M-1) and the colorant that represented by formula (M-2) and the used time, the colorant represented by formula (M-1) is preferably 1:2 ~ 15:1 with the colorant represented by formula (M-2) containing ratio, is more preferably 5:1 ~ 13:1.By containing two dyestuffs with such ratio, there is the trend that can meet wet fastness, ozone resistance with high level.

Magenta ink in order to adjust tone etc., with photostabilization can be in not serious infringement each characteristic of representative scope in containing pinkish red based dye other than the above.

(cyan ink)

Cyan ink contains more than a kind in the colorant being selected from and being represented by following formula (C-1) and following formula (C-2).Cyan ink is preferably containing the colorant represented by following formula (C-1) and following formula (C-2).By containing the colorant represented by following formula (C-1) and following formula (C-2), by the colorant represented by formula (C-2) of use alpha-position substituted type and the colorant represented by formula (C-2) of β-position substituted type, can adjust not in molecule at the ratio of intermolecular α position and β position, as a result, the trend obtaining the image with good fastness and high print concentration is had.

(colorant represented by formula (C-1))

Below, the colorant represented by formula (C-1) is described in detail.

(in formula (C-1),

M ₁represent hydrogen atom, metallic element, metal oxide, metal hydroxides or metal halide.)

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅represent hydrogen atom independently of one another, halogen atom, alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl, heterocyclic radical, cyano group, hydroxyl, nitro, amino, alkylamino, alkoxyl group, aryloxy, amide group, arylamino, urea groups, sulphamoylamino, alkyl sulfenyl, artyl sulfo, alkoxycarbonyl amino, sulfoamido, formamyl, sulfamyl, alkoxy carbonyl, heterocyclic oxy group, azo-group, acyloxy, carbamoyloxy, silyl oxygen base, aryloxycarbonyl, aryloxycarbonylamino, imide, heterocyclethio, phosphoryl, acyl group or ionic hydrophilic radical.These groups can have substituting group further.Alternatively base, can enumerate the substituting group recorded in above-mentioned substituting group group A.

In formula (C-1), as R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅represented halogen atom, can enumerate fluorine atom, chlorine atom and bromine atoms.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented alkyl and there is substituent alkyl and the alkyl without replacement.As alkyl, carbonatoms when preferably not comprising substituting group is the alkyl of 1 ~ 12.Hydroxyl, alkoxyl group, cyano group and halogen atom and ionic hydrophilic radical is comprised in substituent example.Methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfapropyl and 4-sulfobutyl group is comprised in the example of alkyl.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented cycloalkyl and there is substituent cycloalkyl and the cycloalkyl without replacement.As cycloalkyl, carbonatoms when preferably not comprising substituting group is the cycloalkyl of 5 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Cyclohexyl is comprised in the example of cycloalkyl.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented thiazolinyl and there is substituent thiazolinyl and the thiazolinyl without replacement.As thiazolinyl, carbonatoms when preferably not comprising substituting group is the thiazolinyl of 2 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Vinyl, allyl group etc. is comprised in the example of thiazolinyl.

In formula (C-1), as R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅represented aralkyl, comprises and has substituent aralkyl and the aralkyl without replacement.As aralkyl, carbonatoms when preferably not comprising substituting group is the aralkyl of 7 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Benzyl and 2-styroyl is comprised in the example of aralkyl.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented aryl and there is substituent aryl and the aryl without replacement.As aryl, carbonatoms when preferably not comprising substituting group is the aryl of 6 ~ 12.Alkyl, alkoxyl group, halogen atom, alkylamino and ionic hydrophilic radical is comprised in substituent example.Phenyl, p-methylphenyl, p-methoxyphenyl, Chloro-O-Phenyl and (3-sulfopropylamino) phenyl is comprised in the example of aryl.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented heterocyclic radical and there is substituent heterocyclic radical and the heterocyclic radical without replacement.As heterocyclic radical, the preferably heterocyclic radical of 5 yuan or 6 rings.Ionic hydrophilic radical is comprised in substituent example.2-pyridyl, 2-thienyl and 2-furyl is comprised in the example of heterocyclic radical.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented alkylamino and there is substituent alkylamino and the alkylamino without replacement.As alkylamino, carbonatoms when preferably not comprising substituting group is the alkylamino of 1 ~ 6.Ionic hydrophilic radical is comprised in substituent example.Methylamino and diethylamino is comprised in the example of alkylamino.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented alkoxyl group and there is substituent alkoxyl group and the alkoxyl group without replacement.As alkoxyl group when not comprising substituting group, preferred carbonatoms is the alkoxyl group of 1 ~ 12.Alkoxyl group, hydroxyl and ionic hydrophilic radical is comprised in substituent example.Methoxyl group, oxyethyl group, isopropoxy, methoxy ethoxy, hydroxyl-oxethyl and 3-carboxypropoxy is comprised in the example of alkoxyl group.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented aryloxy and there is substituent aryloxy and the aryloxy without replacement.As aryloxy, carbonatoms when preferably not comprising substituting group is the aryloxy of 6 ~ 12.Alkoxyl group and ionic hydrophilic radical is comprised in substituent example.Phenoxy group is comprised, to methoxyphenoxy and o-methoxyphenoxy in the example of aryloxy.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented amide group and there is substituent amide group and the amide group without replacement.As amide group, carbonatoms when preferably not comprising substituting group is the amide group of 2 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Acetamido, propionamido-, benzoylamino and 3,5-disulfobenzene formamido-is comprised in the example of amide group.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented arylamino and there is substituent arylamino and the arylamino without replacement.As arylamino, carbonatoms when preferably not comprising substituting group is the arylamino of 6 ~ 12.The alternatively example of base, comprises halogen atom and ionic hydrophilic radical.As the example of arylamino, comprise anilino and 2-chloroanilino.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented urea groups and there is substituent urea groups and the urea groups without replacement.As urea groups, carbonatoms when preferably not comprising substituting group is the urea groups of 1 ~ 12.Alkyl and aryl is comprised in substituent example.3-methyl urea groups, 3,3-dimethyl urea groups and 3-phenyl urea groups is comprised in the example of urea groups.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented sulphamoylamino and there is substituent sulphamoylamino and the sulphamoylamino without replacement.Alkyl is comprised in substituent example.N is comprised, N-dipropyl sulphamoylamino in the example of sulphamoylamino.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented alkyl sulfenyl and there is substituent alkyl sulfenyl and the alkyl sulfenyl without replacement.As alkyl sulfenyl, carbonatoms when preferably not comprising substituting group is the alkyl sulfenyl of 1 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Methylthio group and ethylmercapto group is comprised in the example of alkyl sulfenyl.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented artyl sulfo and there is substituent artyl sulfo and the artyl sulfo without replacement.As artyl sulfo, carbonatoms when preferably not comprising substituting group is the artyl sulfo of 6 ~ 12.Alkyl and ionic hydrophilic radical is comprised in substituent example.Thiophenyl and p-methylphenyl sulfenyl is comprised in the example of artyl sulfo.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented alkoxycarbonyl amino and there is substituent alkoxycarbonyl amino and the alkoxycarbonyl amino without replacement.As alkoxycarbonyl amino, carbonatoms when preferably not comprising substituting group is the alkoxycarbonyl amino of 2 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Ethoxycarbonylamino group is comprised in the example of alkoxycarbonyl amino.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented sulfoamido and there is substituent sulfoamido and the sulfoamido without replacement.As sulfoamido, carbonatoms when preferably not comprising substituting group is the sulfoamido of 1 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Amsacrine, benzsulfamide and 3-carboxybenzenesulfonamide is comprised in the example of sulfoamido.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented formamyl and there is substituent formamyl and the formamyl without replacement.Alkyl is comprised in substituent example.Methylcarbamoyl and formyl-dimethylamino is comprised in the example of formamyl.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented sulfamyl and there is substituent sulfamyl and the sulfamyl without replacement.Alkyl, aryl is comprised in substituent example.DimethylsuIfamoyl and two-(2-hydroxyethyl) sulfamyl, phenyl sulfamoyl base is comprised in the example of sulfamyl.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented alkoxy carbonyl and there is substituent alkoxy carbonyl and the alkoxy carbonyl without replacement.As alkoxy carbonyl, carbonatoms when preferably not comprising substituting group is the alkoxy carbonyl of 2 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Methoxycarbonyl and ethoxy carbonyl is comprised in the example of alkoxy carbonyl.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented heterocyclic oxy group and there is substituent heterocyclic oxy group and the heterocyclic oxy group without replacement.As heterocyclic oxy group, preferably there is the heterocyclic oxy group of the heterocycle of 5 yuan or 6 rings.Hydroxyl and ionic hydrophilic radical is comprised in substituent example.2-THP trtrahydropyranyl oxygen base is comprised in the example of heterocyclic oxy group.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented azo-group and there is substituent azo-group and the azo-group without replacement.P-nitrophenyl azo-group is comprised in the example of azo-group.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented acyloxy and there is substituent acyloxy and the acyloxy without replacement.As acyloxy, carbonatoms when preferably not comprising substituting group is the acyloxy of 1 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Acetoxyl group and benzoyloxy is comprised in the example of acyloxy.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented carbamoyloxy and there is substituent carbamoyloxy and the carbamoyloxy without replacement.Alkyl is comprised in substituent example.N-methylcarbamoyl oxygen base is comprised in the example of carbamoyloxy.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented silyl oxygen base and there is substituent silyl oxygen base and the silyl oxygen base without replacement.Alkyl is comprised in substituent example.Trimethyl silyl oxygen base is comprised in the example of silyl oxygen base.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented aryloxycarbonyl and there is substituent aryloxycarbonyl and the aryloxycarbonyl without replacement.As aryloxycarbonyl, carbonatoms when preferably not comprising substituting group is the aryloxycarbonyl of 7 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Phenyloxycarbonyl is comprised in the example of aryloxycarbonyl.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented aryloxycarbonylamino and there is substituent aryloxycarbonylamino and the aryloxycarbonylamino without replacement.As aryloxycarbonylamino, carbonatoms when preferably not comprising substituting group is the aryloxycarbonylamino of 7 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Phenoxycarbonylamino is comprised in the example of aryloxycarbonylamino.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented imide and there is substituent imide and the imide without replacement.N phlhalimide base and N-succinimido is comprised in the example of imide.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented heterocyclethio and there is substituent heterocyclethio and the heterocyclethio without replacement.As heterocyclethio, preferably there is the heterocycle of 5 yuan or 6 rings.Ionic hydrophilic radical is comprised in substituent example.2-pyridinylthio is comprised in the example of heterocyclethio.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented phosphoryl and there is substituent phosphoryl and the phosphoryl without replacement.Phenoxy group phosphoryl and diphenylphosphoryl base is comprised in the example of phosphoryl.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅comprise in represented acyl group and there is substituent acyl group and the acyl group without replacement.As acyl group, carbonatoms when preferably not comprising substituting group is the acyl group of 1 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Ethanoyl and benzoyl is comprised in the example of acyl group.

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅sulfo group, carboxyl and quaternary ammonium group etc. are comprised in represented ionic hydrophilic radical.As ionic hydrophilic radical, preferred carboxyl and sulfo group, particularly preferably sulfo group.Carboxyl and sulfo group can be the states of salt, are formed in the example of the counter ion of salt and comprise alkalimetal ion (such as, sodium ion, potassium ion) and organic cation (such as, tetramethyl guanidine ion).

In formula (C-1), R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅especially preferably hydrogen atom, halogen atom, alkyl, aryl, cyano group, alkoxyl group, amide group, urea groups, sulfoamido, formamyl, sulfamyl and alkoxy carbonyl, particularly preferably hydrogen atom, halogen atom, cyano group, most preferably hydrogen atom.

In formula (C-1), Z ₁, Z ₂, Z ₃and Z ₄independently of one another represent replace or without replace alkyl, replacement or without replace cycloalkyl, replacement or without replace thiazolinyl, replacement or without replace aralkyl, replacement or without replace aryl or replace or without replace heterocyclic radical.Wherein, Z ₁, Z ₂, Z ₃and Z ₄in at least 1 there is ionic hydrophilic radical alternatively base.Alternatively base, can enumerate the substituting group recorded in above-mentioned substituting group group A.

In formula (C-1), Z ₁, Z ₂, Z ₃and Z ₄comprise in represented alkyl and there is substituent alkyl and the alkyl without replacement.Carbonatoms when alkyl does not preferably comprise substituting group is the alkyl of 1 ~ 12.Hydroxyl, alkoxyl group, cyano group, alkylamino (RNH-, RR ' N-), formamyl (-CONHR), sulfamyl (-SO is comprised in substituent example ₂nHR ,-SO ₂nRR '), sulfuryl amino (-NHSO ₂r) ,-SONHR base ,-SONRR ' base, halogen atom and ionic hydrophilic radical.(should illustrate, above-mentioned R, R ' represent alkyl, phenyl, they can also have substituting group.Alternatively base, can enumerate alkylamino, hydroxyl, ionic hydrophilic radical etc.R, R ' ring can be formed by chemical bonding.) alkyl example in comprise methyl, ethyl, butyl, n-propyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfapropyl and 4-sulfobutyl group.

In formula (C-1), Z ₁, Z ₂, Z ₃and Z ₄comprise in represented cycloalkyl and there is substituent cycloalkyl and the cycloalkyl without replacement.As cycloalkyl, carbonatoms when preferably not comprising substituting group is the cycloalkyl of 5 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Cyclohexyl is comprised in the example of cycloalkyl.

In formula (C-1), Z ₁, Z ₂, Z ₃and Z ₄comprise in represented thiazolinyl and there is substituent thiazolinyl and the thiazolinyl without replacement.As thiazolinyl, carbonatoms when preferably not comprising substituting group is the thiazolinyl of 2 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Vinyl, allyl group etc. is comprised in the example of thiazolinyl.

In formula (C-1), as Z ₁, Z ₂, Z ₃and Z ₄represented aralkyl, comprises and has substituent aralkyl and the aralkyl without replacement.As aralkyl, carbonatoms when preferably not comprising substituting group is the aralkyl of 7 ~ 12.Ionic hydrophilic radical is comprised in substituent example.Benzyl and 2-styroyl is comprised in the example of aralkyl.

In formula (C-1), Z ₁, Z ₂, Z ₃and Z ₄comprise in represented aryl and there is substituent aryl and the aryl without replacement.As aryl, carbonatoms when preferably not comprising substituting group is the aryl of 6 ~ 12.Phenyl, p-methylphenyl, p-methoxyphenyl, Chloro-O-Phenyl and (3-sulfopropylamino) phenyl, a sulfo group phenyl is comprised in the example of aryl.Alkyl (R-), alkoxyl group (RO-), alkylamino (RNH-, RR ' N-), formamyl (-CONHR), sulfamyl (-SO is comprised in substituent example ₂nHR), sulfuryl amino (-NHSO ₂r), halogen atom, ionic hydrophilic radical (should illustrate, above-mentioned R, R ' represent alkyl, phenyl, they can have ionic hydrophilic radical further).

In formula (C-1), Z ₁, Z ₂, Z ₃and Z ₄represented heterocyclic radical comprises and has substituent heterocyclic radical and without the heterocyclic radical replaced, can also form condensed ring with other rings.As heterocyclic radical, the preferably heterocyclic radical of 5 yuan or 6 rings.Heterocyclic radical can also form condensed ring with other rings.If do not enumerated with not limiting the position of substitution of heterocycle in the example of heterocyclic radical, separately comprise imidazoles, benzoglyoxaline, pyrazoles, benzopyrazoles, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, azoles, benzo azoles, thiadiazoles, diazole, pyrroles, benzopyrrole, indoles, different azoles, benzisoxa azoles, thiophene, thionaphthene, furans, cumarone, pyridine, quinoline, isoquinoline 99.9, pyridazine, pyrimidine, pyrazine, cinnolines, phthalazines, quinazoline, quinoxaline, triazine etc.Alkyl (R-), aryl (R-), alkoxyl group (RO-), alkylamino (RNH-, RR ' N-), formamyl (-CONHR), sulfamyl (-SO is comprised in substituent example ₂nHR), sulfuryl amino (-NHSO ₂r), alkylsulfonyl (-SO ₂r), acyl amino (-NHCOR), halogen atom, ionic hydrophilic radical (should illustrate; above-mentioned R, R ' represent alkyl, aryl, they can have ionic hydrophilic radical further or have the substituting group of ionic hydrophilic radical).

In formula (C-1), Z ₁, Z ₂, Z ₃and Z ₄preferred replacement or without replace alkyl, replacement or without replace aryl, replacement or without replace heterocyclic radical, the heterocyclic radical of the alkyl more preferably replaced, the aryl of replacement, replacement, the alkyl more preferably replaced.

In formula (C-1), Z ₁, Z ₂, Z ₃and Z ₄in at least 1 there is ionic hydrophilic radical alternatively base.Sulfo group, carboxyl and quaternary ammonium group etc. are comprised in the ionic hydrophilic radical of alternatively base.As this ionic hydrophilic radical, preferred carboxyl and sulfo group, particularly preferably sulfo group.Carboxyl and sulfo group can be the states of salt, are formed in the example of the counter ion of salt and comprise alkalimetal ion (such as, sodium ion, potassium ion) and organic cation (such as, tetramethyl guanidine ion).

In formula (C-1), l, m, n and p represent 1 or 2 independently of one another.That is, 4≤l+m+n+p≤8 are met.Preferably meet 4≤l+m+n+p≤6, be most preferably respectively the situation of 1 (l=m=n=p=1).

In formula (C-1), q ₁, q ₂, q ₃and q ₄represent 1 or 2 independently of one another.Be particularly preferably q ₁=q ₂=q ₃=q ₄=2.

In formula (C-1), M ₁represent hydrogen atom, metallic element, metal oxide, metal hydroxides or metal halide.

In formula (C-1), as M ₁preferred example, except hydrogen atom, as metallic element, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi etc. can be enumerated.Wherein particularly preferably Cu, Ni, Zn, Al etc., most preferably Cu.As metal oxide, preferably VO, GeO etc. can be enumerated.In addition, as metal hydroxides, Si (OH) preferably can be enumerated ₂, Cr (OH) ₂, Sn (OH) ₂deng.Further, as metal halide, AlCl, SiCl can be enumerated ₂, VCl, VCl ₂, VOCl, FeCl, GaCl, ZrCl etc.

The content of the colorant represented by formula (C-1), relative to the total amount of cyan ink, is preferably 0.050 ~ 1.0 quality %, is more preferably 0.10 ~ 0.80 quality %, more preferably 0.20 ~ 0.60 quality %.By the content of colorant that represented by formula (C-1) in above-mentioned scope, there is the trend obtaining the image with good fastness and high print concentration.

(colorant represented by formula (C-2))

Below, the colorant represented by formula (C-2) is described in detail.

(in formula (C-2),

M ₂represent hydrogen atom, metallic element, metal oxide, metal hydroxides or metal halide.)

In formula (C-2), R ₁, R ₄, R ₅, R ₈, R ₉, R ₁₂, R ₁₃and R ₁₆independently of one another with the R in above-mentioned formula (C-1) ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅implication is identical respectively.

In formula (C-2), Z ₅, Z ₆, Z ₇and Z ₈independently of one another with the Z in above-mentioned formula (C-1) ₁, Z ₂, Z ₃and Z ₄implication is identical respectively.

In formula (C-2), t, u, v, w, q ₅, q ₆, q ₇and q ₈represent 1 or 2 independently of one another.

In formula (C-2), M ₂with the M in above-mentioned formula (C-1) ₁implication is identical.

In formula (C-2), R ₁, R ₄, R ₅, R ₈, R ₉, R ₁₂, R ₁₃and R ₁₆independently of one another with the R in above-mentioned formula (C-1) ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅implication is identical respectively; preferred hydrogen atom, halogen atom, alkyl, aryl, cyano group, alkoxyl group, amide group, urea groups, sulfoamido, formamyl, sulfamyl and alkoxy carbonyl; particularly preferably hydrogen atom, halogen atom, cyano group, most preferably hydrogen atom.These groups can have substituting group further.Alternatively base, can enumerate the substituting group recorded in above-mentioned substituting group group A.

In formula (C-2), Z ₅, Z ₆, Z ₇and Z ₈preferred replacement or without replace alkyl, replacement or without replace aryl, replacement or without replace heterocyclic radical, the heterocyclic radical of the alkyl more preferably replaced, the aryl of replacement, replacement, the alkyl more preferably replaced.In addition, from the view point of ozone fastness, the alkyl most preferably replaced have substituent at least one for-SONHR base.

In formula (C-2), Z ₅, Z ₆, Z ₇and Z ₈in at least one Z alternatively in base and the ionic hydrophilic radical had and above-mentioned formula (C-1) ₁, Z ₂, Z ₃and Z ₄alternatively base and the ionic hydrophilic radical implication had is identical, preferred example is also identical.

In formula (C-2), t, u, v and w represent 1 or 2 independently of one another.That is, 4≤t+u+v+w≤8 are met.Preferably meet 4≤t+u+v+w≤6, be most preferably respectively the situation of 1 (t=u=v=w=1).

In formula (C-2), q ₅, q ₆, q ₇and q ₈represent 1 or 2 independently of one another.Be particularly preferably q ₅=q ₆=q ₇=q ₈=2.

In formula (C-2), M ₂with the M in above-mentioned formula (C-1) ₁implication is identical, and preferred example is also identical.

The content of the colorant represented by formula (C-2), relative to the total amount of cyan ink, is preferably 2.5 ~ 7.5 quality %, is more preferably 3.0 ~ 5.0 quality %, more preferably 3.5 ~ 4.5 quality %.By the content of colorant that represented by formula (C-2) in above-mentioned scope, there is the trend obtaining the image with good fastness and high print concentration.

The colorant represented by formula (C-1) and formula (C-2), such as can pass through white well-holt outstanding, IPC Co., Ltd. distribution " phthalocyanine-chemistry and function-" (P.1 ~ 62) altogether, C.C.Leznoff-A.B.P.Lever altogether work, VCH issues the middle records such as ' Phthalocyanines-PropertiesandApplications ' (P.1 ~ 54), quotes or synthesize with these similar Combination of Methods.

Below, be described with the example that synthesizes of the colorant represented by formula (C-2).R in the colorant represented by formula (C-2) ₁, R ₄, R ₅, R ₈, R ₉, R ₁₂, R ₁₃and R ₁₆for hydrogen, q ₅, q ₆, q ₇and q ₈be the compound of 2, such as, can react to synthesize with the metal derivative represented by following M-(Y) d by making the phthalonitrile derivatives that represented by following formula (C-2-1) and/or the diiminoisoindole derivative that represented by following formula (C-2-2).

In formula (C-2-1) and/or formula (C-2-2), x is identical with t, u, v, w implication in formula (C-2).Z represents and Z ₅, Z ₆, Z ₇and Z ₈corresponding substituting group.

Y represents the part of 1 valencys such as halogen atom, acetate anion, methyl ethyl diketone root, oxygen or divalent, and d is the integer of 1 ~ 4.

As the metal derivative represented by M-(Y) d, the halogenide of Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, Pb, carboxylic acid derivative, vitriol, nitrate, carbonyl compound, oxide compound, title complex etc. can be enumerated.As concrete example, cupric chloride, cupric bromide, cupric iodide, nickelous chloride, nickelous bromide, nickelous acetate, cobalt chloride, cobaltous bromide, cobaltous acetate, iron(ic) chloride, zinc chloride, zinc bromide, zinc iodide, zinc acetate, vanadium chloride, vanadium oxytrichloride, Palladous chloride, acid chloride, aluminum chloride, Manganous chloride tetrahydrate, manganous acetate, manganese acetylacetonate, Manganous chloride tetrahydrate, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride etc. can be enumerated.

By R in the colorant represented by above-mentioned formula (C-2) obtained like this ₁, R ₄, R ₅, R ₈, R ₉, R ₁₂, R ₁₃and R ₁₆for hydrogen, q ₅, q ₆, q ₇and q ₈be that the phthalocyanine compound (such as: during t=u=v=w=1) of 2 expressions usually becomes and belongs to Ra (SO ₂-Z ₅), Rb (SO ₂-Z ₆), Rc (SO ₂-Z ₇), Rd (SO ₂-Z ₈) the mixture of compound represented by following formula (a)-1 ~ (a)-4 of isomer of each the position of substitution.

That is, the compound represented by above-mentioned formula (C-2-3)-(C-2-6) is that β-position substituted type is (by the R in following formula (C-2) ₁~ R ₁₆when being set to 1 ~ 16 respectively, there is at 2 and/or 3,6 and/or 7,10 and/or 11,14 and/or 15 the phthalocyanine compound of specified substituent).

The colorant represented by formula (C-1) is alpha-position substituted type (having the phthalocyanine compound of specified substituent at 1 and/or 4,5 and/or 8,9 and/or 12,13 and/or 16).

In addition, the colorant represented by formula (C-2) is β-position substituted type (having the phthalocyanine compound of specified substituent at 2 and/or 3,6 and/or 7,10 and/or 11,14 and/or 15).In the present embodiment, in order to good fastness, importantly all have by-SO-Z and/or-SO in any substituted type ₂the specific substituting group that-Z represents.

Use formula (C-2-7) to illustrate following the concrete example of the colorant represented by formula (C-1) or formula (C-2), the phthalocyanine pigment used in present embodiment is not limited to following example.

(illustration of the colorant represented by formula (C-1))

Below ※, (R ₁, R ₄) (R ₂, R ₃) (R ₅, R ₈) (R ₆, R ₇) (R ₉, R ₁₂) (R ₁₀, R ₁₁) (R ₁₃, R ₁₆) (R ₁₄, R ₁₅) the concrete example of each group separately order is different.

(illustration of the colorant represented by formula (C-2))

(black ink)

Ink group can possess at least one party in dyestuff black ink and Pigment black color ink further.

(dyestuff black ink)

Dyestuff black ink preferably containing at least a kind that is selected from the azo-compound or its salt, the colorant represented by following formula (Bw-1), the colorant represented by following formula (b-1) and the colorant represented by following formula (b-3) that are represented by following formula (Bk-1), more preferably containing at least a kind that is selected from the azo-compound or its salt that are represented by following formula (Bk-1) and the colorant represented by following formula (Bw-1).

(azo-compound represented by formula (Bk-1) or its salt)

Below, the azo-compound represented by formula (Bk-1) or its salt are described in detail.

In formula (Bk-1); do not record the carbonatoms in the alkyl, alkoxyl group, acyl group etc. of carbonatoms especially; be not particularly limited in the scope of the effect that can realize present embodiment; usual carbonatoms is about 1 ~ 20, and preferred carbonatoms is about 1 ~ 10, when further preferred alkyl, alkoxyl group or aliphatic acyl group; carbonatoms is about 1 ~ 4; during aromatic acyl group, carbonatoms is 7 ~ 11, specifically can enumerate benzoyl, naphthoyl etc.

In formula (Bk-1), R ¹, R ², R ⁵, R ⁶and R ⁷in; as the example of N-alkyl amino sulfonyl, such as, N-methylaminosulfonyl, N-ethylaminosulfonyl, N-(normal-butyl) amino-sulfonyl, N can be enumerated; N-dimethylamino-sulfonyl, N, N-bis-(n-propyl) amino-sulfonyl etc.

In formula (Bk-1), R ¹, R ², R ⁵, R ⁶and R ⁷in, as the example of the alkyl sulphonyl of the carbonatoms 1 ~ 4 that can be optionally substituted by a hydroxyl group, such as, methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, butyl alkylsulfonyl, hydroxyethyl alkylsulfonyl, 2-hydroxypropyl alkylsulfonyl etc. can be enumerated.

In formula (Bk-1), R ¹, R ², R ⁵, R ⁶and R ⁷in, as the preferred example of acyl group, such as, the alkyl-carbonyl of carbonatoms 1 ~ 4 or the aromatic carbonyl etc. of the C7 ~ C11 such as benzoyl, naphthoyl such as ethanoyl, propionyl, butyryl radicals or isobutyryl can be enumerated.

In formula (Bk-1), R ¹~ R ⁷in, as the example of the alkyl of the carbonatoms 1 ~ 4 that can be replaced by the alkoxyl group of hydroxyl or carbonatoms 1 ~ 4, such as, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, methoxy ethyl, 2-ethoxyethyl group, positive propoxy ethyl, isopropoxyethyl, n-butoxyethyl, methoxy-propyl, ethoxycarbonyl propyl, positive propoxy propyl group, isopropoxy butyl, positive propoxy butyl etc. can be enumerated.

In formula (Bk-1), R ¹~ R ⁷in, as being selected from hydroxyl, the alkoxyl group of carbonatoms 1 ~ 4, the example of the alkoxyl group of the carbonatoms 1 ~ 4 that the substituting group in sulfo group or carboxyl replaces, such as, methoxyl group can be enumerated, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, 2-hydroxyl-oxethyl, 2-hydroxy propyloxy group, 3-hydroxy propyloxy group, methoxy ethoxy, ethoxy ethoxy, positive propoxy oxyethyl group, isopropoxy oxyethyl group, n-butoxy oxyethyl group, methoxy propoxy, oxyethyl group propoxy-, positive propoxy propoxy-, isopropoxy butoxy, positive propoxy butoxy, 2-'-hydroxyethoxy base oxethyl, Carboxvmethoxv, 2-Carboxyethoxy, 3-carboxypropoxy, 3-sulfo group propoxy-, 4-sulfo group butoxy etc.

In formula (Bk-1), R ¹~ R ⁷in; as the preferred acyl group of acyl amino, such as, can enumerate the preferred acyl group enumerated in above-mentioned acyl group one, as preferred acyl amino; such as, acetylamino, propanoylamino, butyryl radicals amino, isobutyrylamino, benzoyl-amido, naphthoyl amino etc. can be enumerated.

In formula (Bk-1), R ¹~ R ⁷in, as the preferred example of alkyl sulfonyl-amino, such as, Methylsulfonylamino, ethylsulphsulphonylamino, propylsulphonylamino etc. can be enumerated.

In formula (Bk-1), R ¹~ R ⁷in, as the preferred example of the phenyl sulfonyl amino that the group that can be selected from halogen atom, alkyl or nitro replaces, such as, BENZENESUFONYLAMINO can be enumerated, tosyl group is amino, chlorobenzenesulfonyl is amino, nitrobenzenesulfonylamino etc.

In formula (Bk-1), preferred R ¹and R ²be hydrogen atom independently of one another, chlorine atom, bromine atoms, cyano group, carboxyl, sulfo group, sulfamyl, N-methylaminosulfonyl, N-phenylaminosulfonyl group, methyl sulphonyl, hydroxyethyl alkylsulfonyl, phosphate, nitro, ethanoyl, benzoyl, urea groups, methyl, methoxyl group, ethyl, oxyethyl group, propyl group, propoxy-, 2-hydroxyl-oxethyl, 2-methoxy ethoxy, 2-ethoxy ethoxy, 3-sulfo group propoxy-, 4-sulfo group butoxy, Carboxvmethoxv, 2-Carboxyethoxy, acetylamino, benzoyl-amido etc., more preferably hydrogen atom, chlorine atom, cyano group, sulfamyl, ethanoyl, nitro, carboxyl or sulfo group, be more preferably hydrogen atom, carboxyl or sulfo group.Preferred R further ¹for carboxyl or sulfo group, particularly preferably sulfo group.R ²particularly preferably hydrogen atom.

In formula (Bk-1), for the position of substitution, R ¹the position of substitution when being ortho position relative to azo-group, the position of substitution of nitro is preferably contraposition relative to azo-group, R ¹the position of substitution when being contraposition relative to azo-group, the position of substitution of nitro is preferably ortho position relative to azo-group.

In formula (Bk-1), preferred R ³and R ⁴be hydrogen atom, cyano group, carboxyl, sulfo group, nitro, methyl, methoxyl group, ethyl, oxyethyl group, propyl group, propoxy-, 2-hydroxyl-oxethyl, 2-methoxy ethoxy, 2-ethoxy ethoxy, 3-sulfo group propoxy-, 4-sulfo group butoxy, Carboxvmethoxv, 2-Carboxyethoxy or acetylamino independently of one another; be more preferably hydrogen atom, carboxyl, sulfo group, methyl, methoxyl group or 3-sulfo group propoxy-, more preferably hydrogen atom or sulfo group.In addition, particularly preferably R ³for sulfo group, R ⁴for the combination of hydrogen atom.

In formula (Bk-1), preferred R ⁵~ R ⁷be hydrogen atom independently of one another, chlorine atom, bromine atoms, cyano group, carboxyl, sulfo group, sulfamyl, N-methylaminosulfonyl, N-phenylaminosulfonyl group, methyl sulphonyl, hydroxyethyl alkylsulfonyl, phosphate, nitro, ethanoyl, benzoyl, urea groups, methyl, methoxyl group, ethyl, oxyethyl group, propyl group, propoxy-, 2-hydroxyl-oxethyl, 2-methoxy ethoxy, 2-ethoxy ethoxy, 3-sulfo group propoxy-, 4-sulfo group butoxy, Carboxvmethoxv, 2-Carboxyethoxy, acetylamino, benzoyl-amido etc., more preferably hydrogen atom, chlorine atom, cyano group, sulfamyl, ethanoyl, nitro, carboxyl or sulfo group, be more preferably hydrogen atom, carboxyl or sulfo group.Particularly preferred R ⁵for hydrogen atom, carboxyl or sulfo group, particularly preferred R ⁶for carboxyl or sulfo group, particularly preferred R ⁷for hydrogen atom.

In formula (Bk-1), as R ¹and R ²preferred example is either party for hydrogen atom or sulfo group and the opposing party is the situation of the alkoxyl group of carboxyl, sulfo group or carbonatoms 1 ~ 4, and more preferably either party is hydrogen atom, the opposing party is the situation of carboxyl or sulfo group.N is 0 or 1, more preferably 1.

In formula (Bk-1), as R ³and R ⁴preferred example is a side is the alkoxyl group of sulfo group or sulfo group carbonatoms 1 ~ 4 and the opposing party is the situation of the alkyl of hydrogen atom, sulfo group or carbonatoms 1 ~ 4, and more preferably a side is sulfo group, the opposing party is the situation of hydrogen atom.In addition, as R ⁵, R ⁶and R ⁷preferred example; any one is the group of the alkyl sulphonyl being selected from sulfo group, carboxyl, sulfo group propoxy-, hydroxyl or hydroxyl carbon atom number 1 ~ 4; more preferably sulfo group or carboxyl; preferred sulfo group further; in addition any one is hydrogen atom, sulfo group, carboxyl, the alkyl of carbonatoms 1 ~ 4, nitro or amino-sulfonyl; be more preferably hydrogen atom, sulfo group or carboxyl, remaining one is hydrogen atom, sulfo group, tosyl group amino or acetylamino, is more preferably hydrogen atom.

More preferably these preferred example combinations each other, the further combination of preferred preferred example and preferred example, most preferably preferred example combination each other.

The salt of the compound represented by formula (Bk-1) is inorganic or organic cationic salt.Wherein as the concrete example of inorganic salt, an alkali metal salt, alkaline earth salt and ammonium salt can be enumerated, preferred inorganic salt are lithium, sodium, the salt of potassium and ammonium salt, in addition, as organic cationic salt, such as can enumerate the salt of the compound that following formula (Bk-2) represents, but be not limited to these.

(in formula (Bk-2), Z ¹, Z ², Z ³, Z ⁴represent alkyl, hydroxyalkyl or hydroxy alkoxy alkyl independently of one another.)

In formula (Bk-2), as Z ¹, Z ², Z ³, Z ⁴the example of alkyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc. can be enumerated.As the example of hydroxyalkyl, the alkyl of the hydroxyl-carbonatomss 1 ~ 4 such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl can be enumerated.As the example of hydroxy alkoxy alkyl, the alkyl of the alkoxyl group-carbonatoms 1 ~ 4 of the hydroxyl carbon atom numbers 1 ~ 4 such as hydroxyethoxymethyl, 2-hydroxyl ethoxy ethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyl-oxethyl butyl, 3-hydroxyl-oxethyl butyl, 2-hydroxyl-oxethyl butyl can be enumerated.The wherein alkyl of preferred hydroxyl-oxethyl-carbonatoms 1 ~ 4.As more preferred example, hydrogen atom can be enumerated; Methyl; The alkyl of the hydroxyl-carbonatomss 1 ~ 4 such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl; The alkyl of the hydroxyl-oxethyl-carbonatomss 1 ~ 4 such as hydroxyethoxymethyl, 2-hydroxyl ethoxy ethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyl-oxethyl butyl, 3-hydroxyl-oxethyl butyl, 2-hydroxyl-oxethyl butyl.

In formula (Bk-2), below Z is shown ¹, Z ², Z ³, Z ⁴concrete example.

Represent that compound can utilize the method manufacture described in Japanese Patent the 4764829th by formula (Bk-1).

As the preferred example of the compound represented by formula (Bk-1), be not particularly limited, specifically can enumerate following structure.

The content of the colorant represented by formula (Bk-1), relative to the total amount of black ink, is preferably 2.5 ~ 7.5 quality %, is more preferably 3.0 ~ 5.0 quality %, more preferably 3.5 ~ 4.5 quality %.By by formula (Bk-1)) content of colorant that represents in above-mentioned scope, have the trend being presented excellent black by visual observation.

(azo-compound represented by formula (Bw-1) or its salt)

Below, the colorant represented by formula (Bw-1) is described in detail.The colorant represented by formula (Bw-1) is the dyestuff of the color correction of the colorant represented by formula (Bk-1).Therefore, by the content of the colorant represented by formula (Bk-1) in adjustment ink and the colorant that represented by formula (Bw-1), these dyestuffs containing ratio, can the tone of image that formed of use ink easily close to Achromatic color.In other words, use the tone of image of ink recording, due to the complementary action of the colorant represented by formula (Bk-1) and the colorant represented by formula (Bw-1), and excellent black can be presented by visual observation.

In this specification sheets, excellent black refers to a of image ^*be worth in the scope of-3 ~ 3, and, b ^*value is-3 ~ 3.Above-mentioned a ^*value and b ^*value is as L ^*a ^*b ^*colour system is specified by CIE (International Commission on Illumination).

In addition, by containing the colorant represented by formula (Bw-1) and the colorant represented by formula (Bk-1) in ink simultaneously, the image of color emissivity excellence can be obtained.Particularly, even if when using the ink containing the colorant represented by formula (Bk-1) and the colorant represented by formula (Bw-1) to carry out the record of image with High Load Rate (duty) value, also not easily cause bronze phenomenon.The phenomenon that " bronze phenomenon " easily causes when referring to and carry out the record of image with High Load Rate value, shows the tone different from original tone or shows metalluster, thus the phenomenon causing color emissivity, tone impaired.

Should illustrate, " rate of load condensate value " refers to by " rate of load condensate (%)=reality ejection counts/(vertical resolving power × horizontal resolving power) × 100 (in formula; " real ejection is counted " is that the actual ejection of per unit area is counted, and " vertical resolving power " and " horizontal resolving power " are respectively the resolving power of per unit area.) " value that calculates.

In addition, the colorant represented by formula (Bw-1) possesses not labile character in ink in the same manner as the colorant represented by formula (Bk-1).Therefore, the excellent storage stability of ink.In addition, the colorant represented by formula (Bw-1) possesses the irradiation being subject to light or gas (particularly ozone) the also not labile character be exposed in air in the same manner as the colorant represented by formula (Bk-1).Therefore, the image using ink to be formed because photostabilization, gas resistance (particularly ozone resistance) are excellent, so not easily cause variable color because of the impact of light, air, fade.Should illustrate, because the colorant represented by formula (Bk-1) and the colorant represented by formula (Bw-1) act synergistically in ink, so improve the storage stability of ink further, or improve the color development concentration, photostabilization, ozone resistance etc. of the image using ink recording further.

In black ink, the content [MA (quality %)] of the colorant represented by formula (Bk-1) is preferably 0.2 ~ 1 with the ratio (MB/MA) of the content [MB (quality %)] of the colorant represented by formula (Bw-1), is more preferably 0.4 ~ 1.If the ratio of the colorant represented by formula (Bk-1) and the content of the colorant to be represented by formula (Bw-1) is in above-mentioned scope, then can obtain the image presenting good black (close to Achromatic color), or the color development concentration of recorded image can be improved or improve photostabilization and gas resistance.

(in above-mentioned formula (Bw-1), R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷and R ²⁸represent hydrogen atom independently of one another; Halogen atom; Sulfo group; Carboxyl; Sulfamyl; Formamyl; The alkyl of carbonatoms 1 ~ 4; The alkoxyl group of carbonatoms 1 ~ 4; By the alkoxyl group being selected from the carbonatoms 1 ~ 4 that at least a kind of group in hydroxyl, the alkoxyl group of carbonatoms 1 ~ 4, the alkoxyl group of hydroxyl carbon atom number 1 ~ 4, sulfo group and carboxyl replaces of alternatively base; The alkyl-carbonyl-amino of carbonatoms 1 ~ 4; By the alkyl-carbonyl-amino of the carbonatoms 1 ~ 4 of carboxyl substituted; Urea groups; The alkyl urea groups of single carbon atom number 1 ~ 4; The alkyl urea groups of two carbonatomss 1 ~ 4; By the alkyl urea groups being selected from the single carbon atom number 1 ~ 4 that at least a kind of group in hydroxyl, sulfo group and carboxyl replaces of alternatively base; By the alkyl urea groups being selected from two carbonatomss 1 ~ 4 that at least a kind of group in hydroxyl, sulfo group and carboxyl replaces of alternatively base; Benzoyl-amido; Phenyl ring is selected from the benzoyl-amido that at least a kind of group in halogen atom, the alkyl of carbonatoms 1 ~ 4, nitro, sulfo group and carboxyl replaces; BENZENESUFONYLAMINO; Or phenyl ring is selected from the phenyl sulfonyl amino that at least a kind of group in halogen atom, the alkyl of carbonatoms 1 ~ 4, nitro, sulfo group and carboxyl replaces.)

In formula (Bw-1), X represents the crosslinked group of divalent.

In formula (Bw-1), as R ²¹~ R ²⁸in halogen atom, fluorine atom, chlorine atom, bromine atoms and atomic iodine can be enumerated.Wherein, preferred fluorine atom, chlorine atom and bromine atoms, particularly preferably chlorine atom.

In formula (Bw-1), as R ²¹~ R ²⁸in the alkyl of carbonatoms 1 ~ 4, the alkyl of straight chain or side chain can be enumerated, the alkyl of preferred straight chain.As the alkyl of carbonatoms 1 ~ 4, such as, the alkyl of the straight chain of methyl, ethyl, n-propyl, normal-butyl and so on can be enumerated; The alkyl of the side chain of sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl and so on.As preferred concrete example, methyl, ethyl can be enumerated, particularly preferably methyl.

In formula (Bw-1), as R ²¹~ R ²⁸in the alkoxyl group of carbonatoms 1 ~ 4, the alkoxyl group of straight chain or side chain can be enumerated.As concrete example, the alkoxyl group of the straight chain of methoxyl group, oxyethyl group, positive propoxy, n-butoxy and so on can be enumerated; The alkoxyl group etc. of the side chain of isopropoxy, isobutoxy, sec-butoxy, tert.-butoxy and so on.As preferred concrete example, methoxyl group, oxyethyl group can be enumerated, particularly preferably methoxyl group.

In formula (Bw-1), as R ²¹~ R ²⁸in by the alkoxyl group being selected from the carbonatoms 1 ~ 4 that at least a kind of group in hydroxyl, the alkoxyl group of carbonatoms 1 ~ 4, the alkoxyl group of hydroxyl carbon atom number 1 ~ 4, sulfo group and carboxyl replaces of alternatively base, can enumerate on any carbon atom in the alkoxyl group of carbonatoms 1 ~ 4 and there is these substituent examples.This substituent number is generally 1 or 2, is preferably 1.Substituent position is not particularly limited, and does not preferably replace the Sauerstoffatom of more than 2 at same carbon atom.As concrete example, the alkoxyl group of the hydroxyl carbon atom numbers 1 ~ 4 such as 2-hydroxyl-oxethyl, 2-hydroxy propyloxy group, 3-hydroxy propyloxy group can be enumerated; The alkoxyl group of the alkoxyl group carbonatoms 1 ~ 4 of the carbonatomss 1 ~ 4 such as methoxy ethoxy, ethoxy ethoxy, positive propoxy oxyethyl group, isopropoxy oxyethyl group, n-butoxy oxyethyl group, methoxy propoxy, oxyethyl group propoxy-, positive propoxy propoxy-, isopropoxy butoxy, positive propoxy butoxy; The alkoxyl group of the alkoxyl group carbonatoms 1 ~ 4 of the hydroxyl carbon atom numbers 1 ~ 4 such as 2-'-hydroxyethoxy base oxethyl; The alkoxyl group of the carboxyl carbon atom numbers 1 ~ 4 such as Carboxvmethoxv, 2-Carboxyethoxy, 3-carboxypropoxy; The alkoxyl group of the sulfo group carbonatomss 1 ~ 4 such as 2-sulfo group oxyethyl group, 3-sulfo group propoxy-, 4-sulfo group butoxy; Deng.

In formula (Bw-1), as R ²¹~ R ²⁸in the alkyl-carbonyl-amino of carbonatoms 1 ~ 4, the alkyl-carbonyl-amino of straight chain or side chain can be enumerated, the alkyl-carbonyl-amino of preferred straight chain.As concrete example, the alkyl-carbonyl-amino of the straight chains such as acetylamino (mentioned methylcarbonylamino), ethylcarbonylamino, propylcarbonylamino, butyl carbonylamino can be enumerated; The alkyl-carbonyl-amino of the side chain such as i propylcarbonylamino, t-butylcarbonylamino; Deng.

In formula (Bw-1), as R ²¹~ R ²⁸in by the concrete example of the alkyl-carbonyl-amino of the carbonatoms 1 ~ 4 of carboxyl substituted, such as, the alkyl-carbonyl-amino of the carboxyl carbon atom numbers 1 ~ 4 such as 2-carboxyethylcarbonyl amino, 3-carboxypropyl carbonylamino can be enumerated; Deng.The replacement number of carboxyl is generally 1 or 2, is preferably 1.

In formula (Bw-1), as R ²¹~ R ²⁸in the alkyl urea groups of single carbon atom number 1 ~ 4, the alkyl urea groups that moieties is straight chain or side chain can be enumerated.The position of substitution of the alkyl of this carbonatoms 1 ~ 4 is not particularly limited, but preferably replaces at " N ' ".In this specification sheets, " the alkyl urea groups of single carbon atom number 1 ~ 4 " refers to " the alkyl NH-CO-NH-of carbonatoms 1 ~ 4 " base or " H ₂n-CO-N (alkyl of carbonatoms 1 ~ 4)-" base, at R ²¹~ R ²⁸in the phenyl ring of bonding, the nitrogen-atoms with this phenyl ring Direct Bonding is designated as " N ", the nitrogen-atoms via carbonyl (CO) base and this nitrogen atom bonding is designated as " N ' ".Therefore, as the position of substitution of the alkyl of this carbonatoms 1 ~ 4, the former is " N ' ", and the latter is " N ".As its concrete example, N '-ethyl urea groups can be enumerated, N '-propylureido, the alkyl urea groups of the straight chains such as N '-butyl urea groups; N '-isopropylureido, N '-isobutyl-urea groups, the alkyl urea groups of the side chains such as N '-tertiary butyl urea groups; Deng.

In formula (Bw-1), as R ²¹~ R ²⁸in the alkyl urea groups of two carbonatomss 1 ~ 4, the alkyl urea groups of straight chain or side chain can be enumerated.The position of substitution of the alkyl of this carbonatoms 1 ~ 4 is not particularly limited, and according to the position of substitution in above-mentioned " the alkyl urea groups of single carbon atom number 1 ~ 4 ", can replace one " N " and " N ' " is each, or " N ' " replace 2, preferred the latter.The alkyl of other 2 these carbonatomss 1 ~ 4 can be identical, also can be different, but preferably identical.'-diethyl urea groups, N ', N '-dipropyl urea groups of as its concrete example, can N ' being enumerated, N '-dimethyl urea groups, N ', N, N ', N ' the alkyl urea groups of the straight chain such as-dibutyl urea groups; The alkyl urea groups of the side chains such as N ', N '-di-isopropyl urea groups, N ', N '-diisobutyl urea groups; Deng.

In formula (Bw-1), as R ²¹~ R ²⁸in by the alkyl urea groups being selected from the single carbon atom number 1 ~ 4 that at least a kind of group in hydroxyl, sulfo group and carboxyl replaces of alternatively base, can enumerate on any carbon atom in the alkyl urea groups of above-mentioned single carbon atom number 1 ~ 4 and there is these substituent alkyl urea groups.This substituent number is generally 1 or 2, is preferably 1.Substituent position is not particularly limited, preferably not at same carbon atom substituted nitrogen atom and hydroxyl.As concrete example, N '-mono-(alkyl of hydroxyl carbon atom number 1 ~ 4) urea groups such as N '-2-hydroxyethyl urea groups, N '-3-hydroxypropyl urea groups can be enumerated; N '-mono-(alkyl of sulfo group carbonatoms 1 ~ 4) urea groups such as N '-2-sulfoethvl urea groups, N '-3-sulfapropyl urea groups; N '-mono-(alkyl of carboxyl carbon atom number 1 ~ 4) urea groups such as N '-carboxymethyl group urea groups, N '-2-carboxy ethyl urea groups, N '-3-carboxypropyl urea groups, N '-4-carboxybutyl urea groups; Deng.

In formula (Bw-1), as R ²¹~ R ²⁸in by the alkyl urea groups being selected from two carbonatomss 1 ~ 4 that at least a kind of group in hydroxyl, sulfo group and carboxyl replaces of alternatively base, can enumerate on any carbon atom in the alkyl urea groups of above-mentioned two carbonatomss 1 ~ 4 and there is these substituent alkyl urea groups.This substituent number is generally 1 or 2, is preferably 2.Substituent position is not particularly limited, preferably not substituted nitrogen atom and hydroxyl on same carbon atom.In addition, when there is multiple substituting group, as its kind, can be the same or different, but preferably identical.As concrete example, N ' can be enumerated, N '-two (2-hydroxyethyl) urea groups, N ', N '-two (2-hydroxypropyl) urea groups, N ', N ', N '-two (alkyl of hydroxyl carbon atom number 1 ~ 4) urea groups such as N '-two (3-hydroxypropyl) urea groups; N ', N '-two (alkyl of sulfo group carbonatoms 1 ~ 4) urea groups such as N ', N '-two (3-sulfapropyl) urea groups; N ', N '-two (alkyl of carboxyl carbon atom number 1 ~ 4) urea groups such as N ', N '-two (carboxymethyl group) urea groups; Deng.

In formula (Bw-1), as R ²¹~ R ²⁸in phenyl ring being selected from halogen atom and (fluorine atom, chlorine atom, bromine atoms and atomic iodine can being enumerated by alternatively base; particularly preferably chlorine atom), the benzoyl-amido that replaces of at least a kind of group in the alkyl of carbonatoms 1 ~ 4, nitro, sulfo group and carboxyl, can enumerate and there is 1 ~ 3, preferably there is 1 or 2 these substituent benzoyl-amido.When there is multiple substituting group, as its kind, can be the same or different, preferably identical.As its concrete example, the halogen atom substituted benzoyls such as 2-chlorobenzoyl-amino, 4-chlorobenzoyl-amino, 2,4 dichloro benzene Formylamino can be enumerated amino; The alkyl substituted benzene Formylamino of the carbonatomss 1 ~ 4 such as 2-methyl benzoyl is amino, 3-methyl benzoyl is amino, 4-methyl benzoyl is amino; 2-nitro benzoyl is amino, 4-nitro benzoyl is amino, 3,5-dinitrobenzoyl amino wait nitro substituted benzoyl amino; The sulfo group substituted benzoyls such as 2-sulfobenzoyl is amino, 4-sulfobenzoyl is amino are amino; The carboxyl substituted benzoyl-amido such as 2-carboxylbenzoyl amino, 4-carboxylbenzoyl amino, 3,5-dicarboxyl benzoyl-amidos; Deng.

In formula (Bw-1), R ²¹~ R ²⁸in; the phenyl sulfonyl amino that at least a kind of group be selected from halogen atom, the alkyl of carbonatoms 1 ~ 4, nitro, sulfo group and carboxyl as phenyl ring replaces, can enumerate and have 1 ~ 3, preferably have 1 or 2, more preferably have 1 these substituent phenyl sulfonyl amino.When there is multiple substituting group, as its kind, can be the same or different.As its concrete example, the halogen atom substituted phenyl sulfonyl bases such as 2-Chlorophenylsulfonyl is amino, 4-Chlorophenylsulfonyl is amino can be enumerated amino; The alkyl-substituted phenyl sulfuryl amino of the carbonatomss 1 ~ 4 such as 2-methylphenylsulfonyl is amino, 4-methylphenylsulfonyl is amino, 4-tert-Butylphenylsulphonyl is amino; The nitro substituted phenyl sulfonyl bases such as 2-nitrophenylsulfonyl is amino, 3-nitrophenylsulfonyl is amino, 4-nitrophenylsulfonyl is amino are amino; The sulfo group substituted phenyl sulfonyl bases such as 3-sulfo group phenyl sulfonyl amino, 4-sulfo group phenyl sulfonyl amino are amino; The carboxyl substituted phenyl sulfuryl aminos such as 3-carboxyl phenyl sulfuryl amino, 4-carboxyl phenyl sulfuryl amino; Deng.

In formula (Bw-1), as R ²¹~ R ²⁸, preferred hydrogen atom; Halogen atom; The alkyl of carbonatoms 1 ~ 4; The alkoxyl group of carbonatoms 1 ~ 4; By the C1-C4 alkoxyl group of sulfo group or carboxyl substituted; The alkyl-carbonyl-amino of carbonatoms 1 ~ 4.Wherein, more preferably hydrogen atom, methyl, ethyl, the tertiary butyl, 2-Carboxyethoxy, 3-carboxypropoxy, 2-sulfo group oxyethyl group, 3-sulfo group propoxy-, 4-sulfo group butoxy.Further, wherein particularly preferably hydrogen atom, methyl, 3-sulfo group propoxy-.

In formula (Bw-1), as R ²¹~ R ²⁸, preferably at least one is the alkoxyl group of the carbonatoms 1 ~ 4 replaced by sulfo group.In addition, more preferably R ²¹~ R ²⁴be separately the alkyl of hydrogen atom, carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4 that replaced by sulfo group, and, R ²¹~ R ²⁴at least one be the alkoxyl group of the carbonatoms 1 ~ 4 replaced by sulfo group, R ²⁵~ R ²⁸it is separately the alkyl of hydrogen atom or carbonatoms 1 ~ 4.In addition, further preferably R ²¹and R ²²in at least one party be sulfo group propoxy-, R ²³and R ²⁴in at least one party be sulfo group propoxy-, R ²⁵~ R ²⁸for the alkyl of carbonatoms 1 ~ 4.

In formula (Bw-1), R ²¹~ R ²⁸the position of substitution be not particularly limited, carry out in the respective phenyl ring replaced at them, using the position of substitution of the nitrogen-atoms with triazine ring bonding as 1, using the position of substitution of azo-group as 4, preferred R ²¹~ R ²⁴replace at 2, R ²⁵~ R ²⁸replace at 5.

In formula (Bw-1), as the crosslinked group representing X, at the compound represented by formula (Bw-1), deliquescent scope is shown to water, as long as the group of divalent is just not particularly limited.Here, as the compound represented by formula (Bw-1) to the solvability of water, relative to the water of 1 liter, the compound represented by formula (Bw-1) dissolves more than 5g usually, more than preferred dissolution 10g, more preferably dissolve more than 25g, further more than preferred dissolution 50g, particularly preferably dissolve more than 100g.As its concrete example, the divalent atoms (heteroatoms of preferred divalent) such as nitrogen-atoms, Sauerstoffatom, sulphur atom can be enumerated; Be respectively the alkylenediamino of C1-C8, alkylenedioxy group or alkylidene group disulfide group; N, N '-hydrazine two base; The replacement on Sauerstoffatom of aminoalkoxyalkyl amino and so on has the example of 2 alkylaminos; And aminoalkoxy Alkoxyalkylamino etc. respectively replaces at the end of the alkylene oxide chain comprising more than 1 ehter bond the example having 1 amino and alkylamino; Deng.Represent the crosslinked group of the divalent of X, as the substituting group of carbon atom, the group be selected from hydroxyl, carboxyl and alkoxyl group can be had; In addition, as the substituting group of nitrogen-atoms, can have moieties can by the alkyl of hydroxyl or carboxyl substituted.

In formula (Bw-1), as the crosslinked group of the divalent of expression X, be preferably selected from C1-C8 alkylenediamino; By the C1-C8 alkylenediamino of hydroxyl or carboxyl substituted; Alkyl-C1-C6 the alkylenediamino of N-carbonatoms 1 ~ 4; Moieties is by the alkyl-C1-C6 alkylenediamino of the N-carbonatoms 1 ~ 4 of hydroxyl or carboxyl substituted; Amino C1-C6 alkoxy C 1-C6 alkylamino; The alkylamino of the alkoxyl group carbonatoms 1 ~ 4 of the alkoxyl group carbonatoms 1 ~ 4 of amino-carbon atomicity 1 ~ 4; Xylylene diamino; Piperazine-Isosorbide-5-Nitrae-two base; By piperazine-Isosorbide-5-Nitrae-two base that the alkoxyl group of the alkyl of carbonatoms 1 ~ 4 or carbonatoms 1 ~ 4 replaces; Or phenylene diamino; In arbitrary group.Should illustrate, the crosslinked group of these divalents is has 2 amino " diamino " groups.Therefore, should " diamino " comprise except piperazine-1, outside a part of groups such as 4-bis-base, by any one nitrogen-atoms carry out being cross-linked (namely, become N, N-bis-base) (that is, becoming N, N '-two base) both situations of being cross-linked of situation or undertaken by different 2 nitrogen-atoms.Wherein, the situation of the latter of " N, N '-two base " is particularly preferably become.

In formula (Bw-1), as the C1-C8 alkylenediamino in X, the alkylenediamino of straight chain or side chain can be enumerated, the alkylenediamino of preferred straight chain.As the scope of carbonatoms, usual C1-C8 can be enumerated, preferred C2-C8, more preferably C2-C6, further preferred C2-C4.As its concrete example, such as, ethylene amino, 1 can be enumerated, 3-propylidene diamino, tetramethylene diamino, pentamethylene diamino, 1, the alkylenediamino of the straight chain of 6-hexylidene diamino, 1,7-sub-heptyl diamino, octamethylene diamino and so on; 2-methyl isophthalic acid, 3-propylidene diamino, 3-methyl isophthalic acid, 4-butylidene diamino, 4-methyl isophthalic acid, the alkylenediamino of the side chains such as 6-hexylidene diamino; Deng.

In formula (Bw-1), as in X by the C1-C8 alkylenediamino of hydroxyl or carboxyl substituted, can enumerate on any carbon atom in above-mentioned C1-C8 alkylenediamino and there is these substituent alkylenediamino.This substituent number is not particularly limited, but is preferably 1 or 2.In addition, when there is multiple substituting group, as its kind, can be the same or different, preferably identical.As its concrete example, such as, the hydroxyls such as 2-hydroxyl-trimethylene diamino, 2-hydroxyl-tetramethylene diamino, 3-hydroxyl-hexamethylene diamino can be enumerated and replace C1-C8 alkylenediamino; 1-carboxyl ethylene is amino, 1-carboxyl-1,3-propylidene diamino, 1-carboxyl-tetramethylene diamino, 1-carboxyl-pentamethylene diamino, 1, the carboxyl substituted C1-C8 alkylenediamino such as 5-dicarboxyl-pentamethylene diamino; Deng.

In formula (Bw-1), as the alkyl-C1-C6 alkylenediamino of the N-carbonatoms 1 ~ 4 in X, refer to the alkylenediamino that the nitrogen-atoms of a side of C1-C6 alkylenediamino is replaced by the alkyl of carbonatoms 1 ~ 4.In this specification sheets, be labeled as in diamino " N " by the nitrogen-atoms that the alkyl of carbonatoms 1 ~ 4 replaces, as required the nitrogen-atoms of the opposing party is labeled as " N ' ".As the scope of the carbonatoms of alkylene moiety, be generally C1-C6, be preferably C2-C4, be particularly preferably C2 or C3.As the alkyl of this carbonatoms 1 ~ 4, the alkyl of straight chain or side chain can be enumerated, the alkyl of preferred straight chain.As its concrete example, the alkyl-C1-C6 alkylenediamino of the N-linear carbon atoms 1 ~ 4 of N-methyl ethylene amino, N-ethylethylene residue diamino, N-propyl group ethylene amino, N-butyl ethylene amino and so on can be enumerated; N-sec.-propyl ethylene is amino, N-isobutyl-ethylene is amino, the alkyl-C1-C6 alkylenediamino of the N-branched carbon atoms number 1 ~ 4 of N-sec-butyl ethylene amino, N-t butylethylidene diamino and so on; Deng.

In formula (Bw-1), moieties in X, by the alkyl-C1-C6 alkylenediamino of the N-carbonatoms 1 ~ 4 of hydroxyl or carboxyl substituted, any carbon atom can enumerating the moieties of the alkyl at N-carbonatoms 1 ~ 4 in the alkyl-C1-C6 alkylenediamino of above-mentioned N-carbonatoms 1 ~ 4 has these substituent examples.Substituent position is not particularly limited, and preferred nitrogen atom and hydroxyl do not replace on same carbon atom.As the scope of the carbonatoms of alkylene moiety, also comprise preferred example, the scope identical with the carbonatoms in the alkyl-C1-C6 alkylenediamino of above-mentioned N-carbonatoms 1 ~ 4 can be enumerated.In addition, as the scope of the carbonatoms of moieties, usual carbonatoms 1 ~ 4, is preferably C2-C4, is more preferably C2-C3.This substituent number is generally 1 or 2, is preferably 1.In addition, when there is multiple substituting group, as its kind, can be the same or different, but preferably identical.As its concrete example, the alkyl-C1-C6 alkylenediamino of the N-hydroxy-substituted carbon atoms numbers 1 ~ 4 such as N-(2-hydroxyethyl) ethylene is amino, N-(3-hydroxypropyl) ethylene is amino, N-(2-hydroxypropyl) ethylene is amino, N-(4-hydroxybutyl) ethylene is amino can be enumerated; Alkyl-C1-C6 the alkylenediamino of the N-carboxyl substituted carbonatomss 1 ~ 4 such as N-(carboxymethyl group) ethylene is amino, N-(2-carboxy ethyl) ethylene is amino, N-(3-carboxypropyl) ethylene is amino, N-(4-carboxybutyl) ethylene is amino; Deng.

In formula (Bw-1), as the amino C1-C6 alkoxy C 1-C6 alkylamino in X, the group of straight chain or side chain can be enumerated, the group of preferred straight chain.Should illustrate, as the group in amino C1-C6 alkoxy C 1-C6 alkylamino with preferred carbon atom number range, amino C2-C4 alkoxy C 2-C4 alkylamino can be enumerated, as the group with particularly preferred carbon atom number range, amino C2-C3 alkoxy C 2-C3 alkylamino can be enumerated.As its concrete example, amino ethoxy ethylamino, amino ethoxy propylcarbamic, amino propoxy-propylcarbamic, amino ethoxy pentyl amino etc. can be enumerated.

In formula (Bw-1), as the alkylamino of the alkoxyl group carbonatoms 1 ~ 4 of the alkoxyl group carbonatoms 1 ~ 4 of the amino-carbon atomicity 1 ~ 4 in X, the group of straight chain or side chain can be enumerated, the group of preferred straight chain.Should illustrate, there is in alkylamino as the alkoxyl group carbonatoms 1 ~ 4 of the alkoxyl group carbonatoms 1 ~ 4 of amino-carbon atomicity 1 ~ 4 group of preferred carbon atom number range, amino C2-C4 alkoxy C 2-C4 alkoxy C 2-C4 alkylamino can be enumerated, as the group with particularly preferred carbon atom number range, amino C2-C3 alkoxy C 2-C3 alkoxy C 2-C3 alkylamino can be enumerated.As its concrete example, can enumerate aminoethyloxyethyloxy ethylamino, amino ethoxy Among is amino, and amino ethoxy butoxyethyl group amino waits the group of straight chain; Amino ethoxy (2-methyl ethoxy) ethylamino, the group of the side chains such as amino ethoxy (2-methyl propoxy-) ethylamino; Deng.

In formula (Bw-1), as the xylylene diamino in X, such as, can enumerate adjacent xylylene diamino, an xylylene diamino, to xylylene diamino, xylylene diamino or to xylylene diamino preferably.

In formula (Bw-1), as piperazine-Isosorbide-5-Nitrae-two base replaced by the alkoxyl group of the alkyl of carbonatoms 1 ~ 4 or carbonatoms 1 ~ 4 in X, can enumerate, on any carbon atom of the ring atom of piperazine ring, there is these substituent groups.This substituent number is generally 1 or 2, is preferably 1.In addition, when there is multiple substituting group, can be the same or different as its kind, preferably identical.As its concrete example, 2-methylpiperazine-1 can be enumerated, 4-bis-base, 2-ethyl piperazidine-Isosorbide-5-Nitrae-two base, 2,5-lupetazins-1,4-bis-base, 2,6-lupetazin-Isosorbide-5-Nitrae-two base, 2,5-diethyl piperazines-1,4-bis-base, 2-methyl-5-ethyl piperazidine-Isosorbide-5-Nitrae-two base; Deng.

In formula (Bw-1), as the phenylene diamino in X, can enumerate neighbour, and to phenylene diamino, preferably or to phenylene diamino.

Above, X is preferably C1-C8 alkylenediamino; By the C1-C8 alkylenediamino of carboxyl substituted; Alkyl-C1-C6 the alkylenediamino of the N-carbonatoms 1 ~ 4 that moieties is optionally substituted by a hydroxyl group; The alkylamino of the alkoxyl group carbonatoms 1 ~ 4 of the alkoxyl group carbonatoms 1 ~ 4 of amino-carbon atomicity 1 ~ 4; Xylylene diamino; Or piperazine-Isosorbide-5-Nitrae-two base.Wherein, X is more preferably C1-C8 alkylenediamino; Xylylene diamino; Or piperazine-Isosorbide-5-Nitrae-two base.As wherein preferred concrete example, ethylene diamino can be enumerated; Trimethylene diamino; Tetramethylene diamino; 1-carboxyl pentylidene-1,5-diamino; N-2-hydroxyethyl-ethylene is amino; Aminoethyloxyethyloxy ethylamino; Between xylylene diamino; Or, piperazine-Isosorbide-5-Nitrae-two base.

In formula (Bw-1), the position of substitution of not specific 4 sulfo groups of the position of substitution is not particularly limited.For in the nuclear substituted sulfo group of the benzene with 1 azo bond, using the position of substitution of this azo bond as 1, can replace at 2,3 or 4, preferably replace at 4.

The compound that the colorant represented by formula (Bw-1) is preferably represented by following formula (Bw-1-1), is more preferably the compound represented by following formula (Bw-1-2).

(in above-mentioned formula (Bw-1-1), R ²¹~ R ²⁸represent and the R in formula (Bw-1) with X ²¹~ R ²⁸the implication identical with X.)

(in above-mentioned formula (Bw-1-2), R ²¹~ R ²⁸represent and the R in formula (Bw-1) with X ²¹~ R ²⁸the implication identical with X.)

For the R in formula (Bw-1) ~ (Bw-1-2) ²¹~ R ²⁸, R in formula (Bw-1) ²¹~ R ²⁸the position of substitution and formula (Bw-1) and formula (Bw-1-1) in the position of substitution etc. of the specific sulfo group of the position of substitution, more preferably by the compound of preferred example combination with one another, the preferred compound that preferred example combination with one another is obtained further.For further preferred example each other, the combination of preferred example and preferred example etc. is also identical.

The salt of the compound represented by formula (Bw-1) can be inorganic or organic cationic salt.As inorganic salt, an alkali metal salt, alkaline earth salt and ammonium salt can be enumerated.Wherein preferred inorganic salt are an alkali metal salt and the ammonium salts such as lithium, sodium, potassium.In addition, as organic cationic salt, such as, the quaternary ammonium ion represented by above-mentioned formula (7) can be enumerated, but be not limited to this.

In addition, free acid and their the various salt of the colorant represented by formula (Bw-1) can be mixtures.Such as, the mixture of the ammonium salt of the colorant that can use the sodium salt of the colorant represented by formula (Bw-1) and represented by formula (Bw-1), the free acid of the colorant represented by formula (Bw-1) and the mixture of the sodium salt of colorant represented by formula (Bw-1), the arbitrary combinations such as the lithium salts of the colorant represented by formula (Bw-1), the sodium salt of colorant represented by formula (Bw-1) and the mixture of the ammonium salt of colorant that represented by formula (Bw-1).According to the kind of salt, the physical property such as solvability are sometimes different, as required by suitably selecting the kind of salt, or changing its ratio containing when multiple salt etc., can obtain the mixture of the physical property with applicable object.

As the preferred concrete example of the colorant represented by formula (Bw-1), be not particularly limited, the compound etc. represented by the following structural formula illustrated can be enumerated.In each table, the functional group such as sulfo group and carboxyl conveniently records with the form of free acid.

The synthetic method of the colorant represented by formula (Bw-1) is not particularly limited, and such as, can use the method recorded in Japanese Unexamined Patent Publication 2012-172031 publication.

The content of the colorant represented by formula (Bw-1), relative to the total amount of black ink, is preferably 0.050 ~ 5.0 quality %, is more preferably 0.10 ~ 3.0 quality %, more preferably 0.50 ~ 1.0 quality %.By the content of colorant that represented by formula (Bw-1) in above-mentioned scope, there is the trend being presented excellent black by visual observation.

(colorant (dyestuff (b-1)) represented by formula (b-1))

Below, the colorant represented by formula (b-1) is described in detail.Dyestuff (b-1) is represented by following general formula (b-1).Dyestuff (b-1) possesses the irradiation being subject to light or gas (particularly ozone) the also not labile character be exposed in air.Therefore, use the image that dyestuff black ink is formed, photostabilization, gas resistance are excellent, not easily cause variable color because of the impact of light, air, fade.

In addition, dyestuff (b-1) possesses the character of excellent moisture resistance.Therefore, not easily there is spreading and sinking in of image because of the impact of moisture etc. to ooze.

The content of dyestuff (b-1), relative to the total mass of dyestuff black ink, is preferably 1 quality % ~ 10 quality %, is more preferably 1 quality % ~ 5 quality %.If the content of dyestuff (b-1) is in above-mentioned scope, then the color development concentration of recorded image be can improve, or photostabilization and gas resistance improved.

In above-mentioned formula (b-1), n is 0 or 1, R ^b11represent carboxyl; C1-C8 alkoxy carbonyl; C1-C4 alkyl; Can by the C1-C4 alkyl of C1-C8 alkoxy carbonyl or carboxyl substituted; Phenyl; Or can by the phenyl of hydroxyl, sulfo group or carboxyl substituted.

In addition, R ^b12, R ^b13and R ^b14represent hydrogen atom independently of one another; Chlorine atom; Hydroxyl; Sulfo group; Carboxyl; Sulfamyl; Formamyl; C1-C4 alkyl; C1-C4 alkoxyl group; By the C1-C4 alkoxyl group of hydroxyl, C1-C4 alkoxyl group, hydroxyl C1-C4 alkoxyl group, sulfo group or carboxyl substituted; By the list of hydroxyl, sulfo group or carboxyl substituted or two C1-C4 alkylaminos; C1-C4 alkyl-carbonyl-amino; By the C1-C4 alkyl-carbonyl-amino of hydroxyl or carboxyl substituted; By the N '-C1-C4 alkyl urea groups of hydroxyl, sulfo group or carboxyl substituted; Phenyl ring is by the phenyl amino of chlorine atom, C1-C4 alkyl, nitro, sulfo group or carboxyl substituted; Phenyl ring is by the benzoyl-amido of chlorine atom, C1-C4 alkyl, nitro, sulfo group or carboxyl substituted; Or phenyl ring is by the BENZENESUFONYLAMINO of chlorine atom, C1-C4 alkyl, nitro, sulfo group or carboxyl substituted.

In addition, A ^b1base is the substituted heterocyclic radical represented by following general formula (b-1-1).

In above-mentioned general formula (b-1-1), R ^b16, R ^b17and R ^b18represent hydrogen atom independently of one another; Chlorine atom; Carboxyl; Sulfo group; Nitro; Hydroxyl; Formamyl; Sulfamyl; C1-C4 alkyl; C1-C4 alkoxyl group; By the C1-C4 alkoxyl group of hydroxyl, C1-C4 alkoxyl group, sulfo group or carboxyl substituted; C1-C4 alkyl sulphonyl; By the C1-C4 alkyl sulphonyl of hydroxyl, sulfo group or carboxyl substituted; Or phenyl ring is by the benzenesulfonyl of chlorine atom, C1-C4 alkyl, nitro, sulfo group or carboxyl substituted.

In addition, B ^b1the naphthyl that base is phenyl or the phenyl be substituted or naphthyl or is substituted.Should illustrate, B ^b1when base is substituted-phenyl, has and be selected from hydroxyl; Sulfo group; Carboxyl; C1-C4 alkyl; C1-C4 alkoxyl group; C1-C4 alkyl sulphonyl; Nitro; Amino; List or two C1-C4 alkylaminos; Acetylamino; And phenyl ring is by the substituting group in the benzoyl-amido of chlorine atom, C1-C4 alkyl, nitro, sulfo group or carboxyl substituted.On the other hand, B ^b1when base is substituted naphthyl, has and be selected from hydroxyl; Sulfo group; C1-C4 alkoxyl group; And the substituting group in the benzenesulfonyl that replaced by methyl, nitro or chlorine atom of phenyl ring.

Dyestuff (b-1) is the compound with tautomer.As tautomer, can enumerate the compound of following general formula (b-1-2) ~ (b-1-4) etc., these tautomers also can use as the dyestuff of present embodiment (b-1).

N, R in above-mentioned general formula (b-1-2) ~ (b-1-4) ^b11, R ^b12, R ^b13, R ^b14, A ^b1base and B ^b1the implication that basis representation is identical with the group in formula (b-1).

R in formula (b-1) ^b11in above-mentioned, preferred carboxyl; C1-C4 alkoxy carbonyl; Without replacing C1-C4 alkyl; Carboxyl substituted C1-C4 alkyl; Or without substituted-phenyl.As R preferred in formula (b-1) ^b11concrete example, be methyl, ethyl, the tertiary butyl, carboxymethyl group, 3-carboxypropyl, carboxyl, phenyl, be more preferably methyl, carboxymethyl group, carboxyl, phenyl, more preferably methyl, carboxyl.

R in general formula (b-1) ^b12~ R ^b14in above-mentioned, preferred hydrogen atom; Sulfo group; Carboxyl; C1-C4 alkyl; C1-C4 alkoxyl group; Or sulfo group replaces N '-C1-C4 alkoxyl group.Preferred R in general formula (b-1) ^b12~ R ^b14concrete example, be hydrogen atom, sulfo group, methyl, methoxyl group, 2-sulfo group oxyethyl group, 3-sulfo group propoxy-, 4-sulfo group butoxy, more preferably hydrogen atom, sulfo group, methyl, methoxyl group, 3-sulfo group propoxy-.

Preferred R in general formula (b-1) ^b12~ R ^b14combination be, R ^b12for 3-sulfo group propoxy-or 4-sulfo group butoxy, R ^b13for hydrogen atom, R ^b14for methyl.

R in general formula (b-1-1) ^b16~ R ^b18in above-mentioned, preferred hydrogen atom; Chlorine atom; Carboxyl; Sulfo group; Nitro; C1-C4 alkyl; C1-C4 alkoxyl group; C1-C4 alkyl sulphonyl.Preferred R in general formula (b-1-1) ^b16~ R ^b18concrete example, be hydrogen atom, chlorine atom, carboxyl, sulfo group, nitro, methyl, methoxyl group, methyl sulphonyl, more preferably hydrogen atom, sulfo group, methoxyl group.In addition, R ^b16~ R ^b18in, preferably at least one is hydrogen atom, and preferably at least one is the substituting group beyond hydrogen atom.

Preferred R in general formula (b-1-1) ^b16, R ^b17, R ^b18combination be hydrogen atom, methoxyl group and sulfo group; Or one for sulfo group and another two is hydrogen atom.One for sulfo group and another two when being hydrogen atom, the position of substitution of sulfo group is more preferably 6 of benzothiazole ring.

In general formula (b-1), B ^b1the phenyl that base is phenyl or is substituted, B ^b1when base is substituted-phenyl, has and be selected from hydroxyl; Sulfo group; Carboxyl; C1-C4 alkyl; C1-C4 alkoxyl group; Amino; List or two C1-C4 alkylaminos; Acetylamino; Phenyl ring is by the substituting group in the benzoyl-amido of chlorine atom, C1-C4 alkyl, nitro, sulfo group or carboxyl substituted.

B in general formula (b-1) ^b1base, for having substituent phenyl, when this substituting group is C1-C4 alkoxyl group, this alkoxyl group, also comprises the R of preferred example and general formula (b-1) ^b12~ R ^b14for the situation without the C1-C4 alkoxyl group replaced is identical.

B in general formula (b-1) ^b1base be single or two C1-C4 alkylamino substituted-phenyls time, this list or two C1-C4 alkylaminos, also comprise preferred example, with the R of general formula (b-1) ^b12~ R ^b14for the situation without the list replaced or two C1-C4 alkylaminos is identical.

In preferred formula (b-1), n is the situation of 1.

B in general formula (b-1) ^b1base in above-mentioned, the phenyl be preferably substituted, the preferred hydroxyl of this substituting group; Sulfo group; Carboxyl; C1-C4 alkyl; C1-C4 alkoxyl group.B in general formula (b-1) ^b1preferred substituent concrete example when base is substituted-phenyl is hydroxyl, sulfo group, carboxyl, methyl, methoxyl group, more preferably sulfo group, carboxyl.

Preferred B in general formula (b-1) ^b1the concrete example of base, for 4-sulfo group phenyl, 2,4-disulfophenyl, 4-carboxyl phenyl, 3,5-dicarboxyphenyi, 4-aminomethyl phenyl, 5-sulfo group-3-carboxyl-2-hydroxy phenyl, 4-p-methoxy-phenyl, be more preferably 4-sulfo group phenyl, 4-carboxyl phenyl, 3,5-dicarboxyphenyi.

The compound of the preferred example the combination with one another more preferably substituting group of mutual-through type (b-1) and (b-1-1) ~ (b-1-4) recorded, preferred by the compound of preferred example combination with one another further.Should illustrate, for the situation by further preferred example combination with one another etc. too.In addition, as mentioned above, n, R in general formula (b-1-2) ~ (b-1-4) ^b11~ R ^b14, A ^b1base and B ^b1the implication that basis representation is identical with the group in general formula (b-1).

The salt of the compound represented by general formula (b-1) is inorganic or organic cationic salt.As the concrete example of inorganic salt, an alkali metal salt, alkaline earth salt and ammonium salt etc. can be enumerated.As wherein preferred inorganic salt, be salt and the ammonium salt of lithium, sodium, potassium.

In addition, the free acid of the dyestuff (b-1) of present embodiment, its tautomer and their various salt can be mixtures.Such as, the mixture of the sodium salt of dyestuff (b-1) and the ammonium salt of dyestuff (b-1) can be used, the mixture of the sodium salt of the free acid and direct dyes (b-1) of dyestuff (b-1), the arbitrary combination such as the mixture of the ammonium salt of the lithium salts of the 1st dyestuff, the sodium salt of dyestuff (b-1) and dyestuff (b-1).According to the kind of salt, the physics value such as solvability is different sometimes, therefore, suitably can select the kind of salt as required, or when containing when multiple salt etc. by its ratio of change etc., thus obtain the mixture of the physical property with applicable object.

As the preferred concrete example of dyestuff (b-1), be not particularly limited, the compound etc. represented by the structural formula shown in following table can be enumerated.In each table, the functional group such as sulfo group and carboxyl conveniently records with the form of free acid.

(colorant (dyestuff (b-3)) represented by formula (b-3))

Below, the colorant represented by formula (b-3) is described in detail.When dyestuff black ink contains dyestuff (b-3), the content [MA (quality %)] of dyestuff (b-1) is preferably 0.5 ~ 1.5 with the ratio (MC/MA) of the content [MC (quality %)] of dyestuff (b-3), is more preferably 0.7 ~ 1.3.If the ratio of the content of dyestuff (b-1) and dyestuff (b-3) is in above-mentioned scope, then more easily can obtain the image presenting good black (close to Achromatic color), the colorrendering quality of recorded image can be improved, improve photostabilization.

In above-mentioned general formula (b-3), R ^b31represent halogen atom; Hydrogen atom; SO ₃m; Or COOM.In addition, R ^b32and R ^b33respective independent expression ground hydrogen atom; SO ₃m; Or COOM.In addition, M ^b3represent at least one party in Li and Na independently of one another.Wherein, in general formula (b-3), R is not had ^b32and R ^b33be the situation of hydrogen atom.

As the compound represented by general formula (b-3), such as, the compound represented by following general formula (b-31) can be enumerated, the compound represented by following general formula (b-32), and the compound represented by following general formula (b-33).Should illustrate, these compounds represented by general formula (b-31) ~ (b-33), can only be used alone a kind, also can mix two or more and use, preferably be used alone the compound represented by general formula (b-31).

In general formula (b-31), M ^b3represent at least one party in Li and Na independently of one another.

In general formula (b-32), M ^b3represent at least one party in Li and Na independently of one another.

In general formula (b-33), M ^b3represent at least one party in Li and Na independently of one another.

(Pigment black color ink)

As the pigment used in Pigment black color ink, be not particularly limited, such as, can No.2300 be enumerated, No.900, MCF88, No.33, No.40, No.45, No.52, MA7, MA8, MA100, No.2200B etc. (more than, Mitsubishi chemical Co., Ltd (MitsubishiChemicalCorporation) makes), Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700 etc. (more than, CarbonColumbia Inc.), Rega1400R, Rega1330R, Rega1660R, MogulL, Monarch700, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400 etc. (CABOTJAPANK.K. Inc.), ColorBlackFW1, ColorBlackFW2, ColorBlackFW2V, ColorBlackFW18, ColorBlackFW200, ColorB1ackS150, ColorBlackS160, ColorBlackS170, Printex35, PrintexU, PrintexV, Printex140U, SpecialBlack6, SpecialBlack5, SpecialBlack4A, SpecialBlack4 (more than, Degussa Inc.).

Pigment black color ink is preferably containing self-dispersing pigments." self-dispersing pigments " refers to and does not disperse with can having dispersion agent or dissolve pigment in an aqueous medium.Here " do not disperse with there is no dispersion agent or dissolve in an aqueous medium " even if refer to the dispersion agent do not used for dispersed color, utilizing the hydrophilic group on its surface to be stably present in state in aqueous medium yet.Therefore, the foaming caused by the defoaming almost do not caused by dispersion agent reduces, has the trend of the ink of easily preparation ejection excellent in stability.In addition, be inhibited because the significantly viscosity caused by dispersion agent rises, so pigment can be contained more, fully can improve and print concentration etc., have operation to become easy trend.

As above-mentioned hydrophilic group, be not particularly limited, such as, can enumerate and be selected from-OM ,-COOM ,-CO-,-SO ₃m ,-SO ₂m ,-SO ₂nH ₂,-RSO ₂m ,-PO ₃hM ,-PO ₃m ₂,-SO ₂nHCOR ,-NH ₃and-NR ₃in more than one hydrophilic group.

Should illustrate, in these chemical formulas, M represents hydrogen atom, basic metal, ammonium, can have substituent phenyl or organic ammonium, and R represents the alkyl of carbonatoms 1 ~ 12 or can have substituent naphthyl.In addition, above-mentioned M and R selects respectively independently of each other.

Self-dispersing pigments, such as, by implementing physical treatment or chemical treatment to pigment, making the surface bond of hydrophilic group and pigment (grafting) and manufacturing.As this physical treatment, such as, vacuum plasma treatment etc. can be illustrated.In addition, as this chemical treatment, such as can be illustrated in water utilize oxygenant to carry out being oxidized wet oxidation process, by making para-amino benzoic acid and surface of pigments bonding and via the method etc. of phenyl and carboxylic-bond.

(composition beyond colorant)

Below, the composition beyond the colorant that can contain in Yellow ink, magenta ink, cyan ink and black ink (referring to all, referred to as " ink ") is described.

(carbonatoms of main chain is the oxirane affixture of the alkyne diol of more than 12 and the carbonatoms of main chain is the alkyne diol of more than 10)

Yellow ink, magenta ink, cyan ink or the carbonatoms of black ink preferably containing main chain used as required are the oxirane affixture of the alkyne diol of more than 12 and the carbonatoms of main chain is the alkyne diol of more than 10.Be the alkyne diol of more than 10 by the carbonatoms of the oxirane affixture containing alkyne diol and main chain, have colorrendering quality, bleeding is inhibited, image quality improves further trend.

(carbonatoms of main chain is the oxirane affixture of the alkyne diol of more than 12)

The carbonatoms of main chain be oxirane affixture (hereinafter also referred to as " alkyne diol A ") and the carbonatoms of main chain described later of the alkyne diol of more than 12 be more than 10 alkyne diol together be contained in alkyne diol system tensio-active agent (nonionic system tensio-active agent).Nonionic system tensio-active agent has the effect of evenly expansion ink on printing medium.Therefore, when using the ink containing nonionic system tensio-active agent to carry out ink-vapor recording, obtain spreading and sinking in and ooze the image of few comparison fine.Should illustrate, " main chain " in this specification sheets refers to the main chain based on IUPAC nomenclature.

Particularly by making the carbonatoms of the main chain of alkyne diol A be more than 12, thus excellent to the wettability of the polymer member such as rubber, plastics forming ink flow path and the foreign matter that can become the factor that bubble in ink produces.Therefore, by using alkyne diol A, the gas bubbles left produced in the stream face of the polymer member from ink tank to shower nozzle can be suppressed.In addition, thus, initial fillibility is excellent, and, the growth of the bubble remained can be prevented and by being attached to the disengaging of bubble in stream face and the leak source that causes, therefore continuous printing stability becomes good simultaneously.Further, be oxirane affixture by alkyne diol A, thus the solvability in ink become excellent.

In order to above-mentioned wettability is more excellent, HLB (Hydrophile-LipophileBalance) value of alkyne diol A is preferably 8 ~ 15.Should illustrate, HLB value is the HLB value of Griffin (Griffin) method definition here.

As alkyne diol A, be not limited to following, such as, the compound represented by following formula (1) can be enumerated.

(in above-mentioned formula (1), R ¹, R ^{1 '}, R ²and R ^{2 '}represent the alkyl of carbonatoms 1 ~ 5 independently of each other, the carbonatoms of main chain is more than 12 ,-OR ³represent-OH or-O (C ₂h ₄o) _mh ,-OR ^{3 '}represent-OH or-O (C ₂h ₄o) _nh.At this moment, m and n is the value comprising decimal of 0.5 ~ 25 independently of each other, m+n be 1 ~ 40 the value comprising decimal (wherein, do not comprise-OR ³with-OR ^{3 '}be the situation of-OH.)。)

As the concrete example of alkyne diol A, be not particularly limited, such as, the ethoxylate of 2,5,8,11-tetramethyl--6-dodecyne-5,8-glycol and the ethoxylate of 5,8-dimethyl-6-dodecyne-5,8-glycol can be enumerated.The preferred ethylene oxide adduct of alkyne diol and the propylene oxide adduct of alkyne diol, the more preferably ethylene oxide adduct of alkyne diol in the oxirane affixture of above-mentioned alkyne diol.

The addition mole number of the alkylene oxide unit in alkyne diol is at R ³and R ^{3 '}separately, be preferably 1 ~ 20 mole.In addition, the sum (R of this addition mole number ³and R ^{3 '}total) be preferably 2 ~ 40 moles.If the addition mole number of alkylene oxide add up to less than 40 moles, then can reduce Static and dynamic surface tension, the absorptive character of ink become good.

As the commercially available product of alkyne diol A, be not limited to following, such as, OLFINEEXP4300 (Nishin Chemical Industry Co. Lt (NissinChemicalIndustryCO. can be enumerated, Ltd.) trade(brand)name processed, carbonatoms 12, ethylene oxide adduct).

Alkyne diol A can be used alone a kind, also can combine two or more and use.

The content of the alkyne diol A contained in Yellow ink, magenta ink, cyan ink or the black ink that uses as required is relative to the total amount of ink, be preferably 0.050 ~ 1.0 quality %, be more preferably 0.075 quality % ~ 0.50 quality %, more preferably 0.10 ~ 0.30 quality %.Be more than 0.050 quality % by the content of alkyne diol A, thus have and the wettability of hydrophobic surface is improved and trend that fillibility improves further.In addition, be below 0.30 quality % by the content of alkyne diol A, thus the trend having steady dissolution to improve further.

The content of the alkyne diol A contained in preferred Yellow ink is more than the content of the alkyne diol A contained in magenta ink or cyan ink.Thus, spreading and sinking between color is had to ooze the further trend improved of balance.

(carbonatoms of main chain is the alkyne diol of more than 10)

The carbonatoms of main chain is that the alkyne diol of more than 10 is (hereinafter also referred to as " alkyne diol B ".), the bubble froth breaking effectively produced in ink can be made.Thus, initial fillibility and continuous printing excellent in stability.

In order to make defoaming excellent, the HLB value of alkyne diol B preferably less than 7, more preferably 3 ~ 5.

As alkyne diol B, be not particularly limited, such as, the alkyne diol represented by following formula (2) can be enumerated.

(in above-mentioned formula (2), R ¹, R ^{1 '}, R ²and R ^{2 '}represent the alkyl of carbonatoms 1 ~ 5 independently of each other, the carbonatoms of main chain is more than 10.Should illustrate, the R in this formula (2) ¹, R ^{1 '}, R ²and R ^{2 '}with the R in above-mentioned formula (1) ¹, R ^{1 '}, R ²and R ^{2 '}it doesn't matter.)

As the concrete example of alkyne diol B, be not limited to following, preferably can enumerate 2,5,8,11-tetramethyl--6-dodecyne-5,8-glycol, 5,8-dimethyl-6-dodecyne-5,8-glycol, 2,4,7,9-tetramethyl--5-decine-4,7-glycol and 4,7-dimethyl-5-decine-4,7-glycol.

As the commercially available product of alkyne diol B, be not limited to following, such as, Surfynol104PG50 (2 can be enumerated, 4,7,9-tetramethyl--5-decine-4,7-glycol), SurfynolDF110D (2,5,8,11-tetramethyl--6-dodecyne-5,8-glycol) (more than, AirProducts Inc. trade(brand)name).

Alkyne diol B can be used alone a kind, also can combine two or more and use.

The content of the alkyne diol B contained in Yellow ink, magenta ink, cyan ink or the black ink that uses as required is relative to the total amount of ink, be preferably 0.050 ~ 1.0 quality %, be more preferably 0.075 ~ 0.50 quality %, more preferably 0.10 ~ 0.30 quality %.Be more than 0.050 quality % by the content of alkyne diol B, have and press down the trend that bubble property improves, fillibility improves further.In addition, be below 0.30 quality % by the content of alkyne diol B, thus the trend having steady dissolution to improve further.

The alkyne diol A contained in Yellow ink, magenta ink, cyan ink or the black ink that uses as required and the total content of alkyne diol B are relative to the total amount of ink, be preferably 0.10 ~ 0.60 quality %, be more preferably 0.10 ~ 0.50 quality %, more preferably 0.20 ~ 0.45 quality %.By the total content of alkyne diol A and alkyne diol B in above-mentioned scope, then to the favorable solubility of ink, when can effectively prevent from coordinating these alkyne diol, produce condensation product.

(polyoxyalkylene alkyl)

Yellow ink, magenta ink, cyan ink or the black ink used as required can contain polyoxyalkylene alkyl.By containing polyoxyalkylene alkyl, there are the solvability of alkyne diol A and alkyne diol B, the dispersed trend improved further.In addition, polyoxyalkylene alkyl not easily impacts the low dynamic surface tension that alkyne diol A and alkyne diol B has.

But ink continuous flow system (CISS) uses the ink flow path, the ink tank that are made up of hydrophobic material mostly, therefore, in the ink group used in ink continuous flow system, each ink uses more hydrophobic tensio-active agent to be effective.From this viewpoint, and be effective with alkyne diol A and alkyne diol B, from the effect obtaining alkyne diol A and alkyne diol B, improve steady dissolution, the initially viewpoint of fillibility, continuous printing stability further to set out simultaneously, when particularly using the ink group of present embodiment to the recording unit possessing ink continuous flow system (CISS), preferred ink contains polyoxyalkylene alkyl.

Here, " ink supply system " refers to the system possessing following mechanism: the ink accepting container (ink tank) with air induction port; Have the printhead of the nozzle of the aforesaid liquid ejection in ink accepting container; Connect above-mentioned ink accepting container and above-mentioned printhead, from above-mentioned ink accepting container to the inking road of above-mentioned printhead supply aforesaid liquid.

In addition, " ink flow path " refers in ink-jet recording device the stream that ink is circulated.As ink flow path, such as, can enumerate for supplying the inking road of ink, the stream for making ink flow pass to nozzle opening portion in ink jet recording head from the ink accepting container stockpiling ink to ink jet recording head.

The HLB value of polyoxyalkylene alkyl is preferably 11 ~ 16, is more preferably 12 ~ 15.By the HLB value of polyoxyalkylene alkyl in above-mentioned scope, there is the trend that initial fillibility and continuous printing stability improve further.

As polyoxyalkylene alkyl, be not limited to following, such as, the compound represented by following formula (3) can be enumerated.By using such polyoxyalkylene alkyl, there is the trend that storage stability and continuous printing stability improve further.

R ⁶O(C ₂H ₄O) _w(C ₃H ₆O) _x(C ₂H ₄O) _y(C ₃H ₆O) _zH···(3)

(in above-mentioned formula (3), R ⁶represent the alkyl of carbonatoms 1 ~ 20, preferably represent the alkyl of carbonatoms 5 ~ 15, more preferably represent the alkyl of carbonatoms 10 ~ 15.In addition, w is the value of 1 ~ 20, and x, y and z are the value of 0 or 1 ~ 20 independently of each other.Further, w, x, y and z meet 5≤w+x+y+z≤30, preferably meet 5≤w+x+y+z≤25.)

As polyoxyalkylene alkyl, be not particularly limited, specifically, can C be enumerated ₁₂h ₂₅o (C ₂h ₄o) ₆(C ₃h ₆o) ₂(C ₂h ₄o) ₆(C ₃h ₆o) ₈h, C ₁₃h ₂₇o (C ₂h ₄o) ₆(C ₃h ₆o) ₂(C ₂h ₄o) ₆(C ₃h ₆o) ₈h, C ₁₂h ₂₅o (C ₂h ₄o) _w(C ₃h ₆o) _x(C ₂h ₄o) _y(C ₃h ₆o) _zh (here, w+y=15, x+z=4), C ₁₃h ₂₇o (C ₂h ₄o) _w(C ₃h ₆o) _x(C ₂h ₄o) _y(C ₃h ₆o) _zh (here, w+y=15, x+z=4), C ₁₂h ₂₅o (C ₂h ₄o) ₈(C ₃h ₆o) ₂(C ₂h ₄o) ₆h, C ₁₃h ₂₇o (C ₂h ₄o) ₈(C ₃h ₆o) ₂(C ₂h ₄o) ₆h, C ₁₂h ₂₅o (C ₂h ₄o) ₁₂(C ₃h ₆o) ₂(C ₂h ₄o) ₁₂h, C ₁₃h ₂₇o (C ₂h ₄o) ₁₂(C ₃h ₆o) ₂(C ₂h ₄o) ₁₂h, CH ₃(CH ₂) ₉(CH ₃) CHO (C ₂h ₄o) ₇(C ₃h ₆o) _4.5h, CH ₃(CH ₂) ₁₁(CH ₃) CHO (C ₂h ₄o) ₇(C ₃h ₆o) _4.5h, CH ₃(CH ₂) ₉(CH ₃) CHO (C ₂h ₄o) ₅(C ₃h ₆o) _3.5h, CH ₃(CH ₂) ₁₁(CH ₃) CHO (C ₂h ₄o) ₅(C ₃h ₆o) _3.5h, C ₁₄h ₂₉o (C ₂h ₄o) ₁₄(C ₃h ₆o) ₂h, C ₁₁h ₂₃o (C ₂h ₄o) ₈h, C ₁₀h ₂₁o (C ₂h ₄o) ₁₁h and C ₁₂h ₂₅o (C ₂h ₄o) ₁₅h.

As the commercially available product of polyoxyalkylene alkyl, be not particularly limited, specifically, NoigenDL-0415 (R can be enumerated ⁶o (C ₂h ₄o) _w(C ₃h ₆o) _x(C ₂h ₄o) _y(C ₃h ₆o) _zh, " R ⁶": the alkyl of carbonatoms 12,13, w+y=15, x+z=4, HLB value 15.0), NoigenET-116B (R ⁶o (C ₂h ₄o) ₇(C ₃h ₆o) _4.5h, " R ⁶": the alkyl of carbonatoms 12,14, HLB value 12.0), NoigenET-106A (R ⁶o (C ₂h ₄o) ₅(C ₃h ₆o) _3.5h, " R ⁶": the alkyl of carbonatoms 12,14, HLB value 10.9), NoigenDH-0300 (R ⁶o (C ₂h ₄o) ₂h, " R ⁶": the alkyl of carbonatoms 14, HLB value 4.0), NoigenYX-400 (R ⁶o (C ₂h ₄o) ₄₀h, " R ⁶": the alkyl of carbonatoms 12, HLB value 18.1), NoigenEA-160 (C ₉h ₁₉c ₆h ₄o (C ₂h ₄o) _16.8h, HLB value 15.4) (more than, the first industrial pharmaceutical Inc.) and Emulgen1108 (KAO. Corp. SA's trade(brand)name, R ⁶o (C ₂h ₄o) ₈h, " R ⁶": the alkyl of carbonatoms 11, HLB value 13.4).

Polyoxyalkylene alkyl can be used alone a kind, also can combine two or more and use.

The content of the polyoxyalkylene alkyl contained in Yellow ink, magenta ink, cyan ink or the black ink that uses as required is relative to the total amount of ink, be preferably 0.010 ~ 0.50 quality %, be more preferably 0.050 ~ 0.30 quality %, more preferably 0.10 ~ 0.30 quality %.By the content of polyoxyalkylene alkyl in above-mentioned scope, there is the trend that storage stability and continuous printing stability improve further.

In addition, the content of polyoxyalkylene alkyl, relative to content 1 mass parts of alkyne diol A, is preferably 0.10 ~ 1.0, is more preferably 0.30 ~ 0.70.By the content of polyoxyalkylene alkyl in above-mentioned scope, there is the abundant solubilization of alkyne diol A, water-solublely become good trend.Therefore, the absorptivity that can suppress to produce condensation product or ink when coordinating is had to produce the trend of deviation.

Further, the content of polyoxyalkylene alkyl, relative to total content 1 mass parts of alkyne diol A and alkyne diol B, is preferably 0.10 ~ 0.5, is more preferably 0.10 ~ 0.40.By the content of polyoxyalkylene alkyl in above-mentioned scope, alkyne diol A and the abundant solubilization of alkyne diol B and water-solublely become good.Therefore, the absorptivity that can suppress to produce condensation product or ink when coordinating polyoxyalkylene alkyl and alkyne diol A and alkyne diol B is had to produce the trend of deviation.

(tensio-active agent other than the above)

The ink used in present embodiment is preferably containing tensio-active agent.As this tensio-active agent, be not particularly limited, such as, in preferred fluorine system tensio-active agent and silicone based surfactants at least any one.Contain these tensio-active agents by ink, the drying property being attached to the ink of cloth and silk becomes better, and, can high speed printing.

Wherein, in ink, more not easily produce foreign matter because of becoming large to the solubleness of ink, so more preferably silicone based surfactants.

As fluorine system tensio-active agent, be not particularly limited, such as, fluorinated alkyl sulfonate, perfluoroalkyl carboxylate, perfluoralkyl phosphate, perfluoroalkyl ethylene oxide affixture, perfluoroalkyl betain, perfluoroalkyl amine oxide compounds can be enumerated.As the commercially available product of fluorine system tensio-active agent, be not particularly limited, such as, S-144, S-145 (Asahi Glass Co., Ltd's system) can be enumerated; FC-170C, FC-430, Fluorad-FC4430 (Sumitomo3M Co., Ltd. system); FSO, FSO-100, FSN, FSN-100, FS-300 (Dupont Inc.); FT-250,251 (Neos Co., Ltd. systems) etc.Fluorine system tensio-active agent can be used alone or two or more kinds may be used.

As silicone based surfactants, polysiloxane based compound, organic silicon modified by polyether oxygen alkane etc. can be enumerated.As the commercially available product of silicone based surfactants, be not particularly limited, specifically, BYK-306 can be enumerated, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349 (above trade(brand)name, BYKJapan Co., Ltd. system), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (above trade(brand)name, KCC of SHIN-ETSU HANTOTAI system) etc.

The content of tensio-active agent, relative to the total mass of ink, is preferably 0.1 ~ 5 quality %, is more preferably 0.1 ~ 3 quality %.By the content of tensio-active agent in above-mentioned scope, there is the trend that the wettability of the ink being attached to printing medium improves further.

(solvent)

Ink can contain solvent further.As solvent, be not particularly limited, such as, can with an organic solvent or water.

As water, such as, the pure water such as ion exchanged water, ultrafiltration water, reverse osmosis water and distilled water can be enumerated, and doing one's utmost as ultrapure water eliminates the water of ionic impurity.In addition, carried out the water of sterilizing if used by irradiation ultraviolet radiation or interpolation hydrogen peroxide etc., then can prevent the generation of mould, bacterium when preserving ink for a long time.Thus, the trend having storage stability to improve further.

In organic solvent, more preferably volatile water-miscible organic solvent.As organic solvent, be not particularly limited, specifically, can glycerine be enumerated, ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-PD, 1,2-butyleneglycol, 1,2-pentanediol, 1,2-hexylene glycol, BDO, 1,5-PD, 1,6-hexylene glycol, Diethylene Glycol list-positive propyl ether, ethylene glycol list-isopropyl ether, Diethylene Glycol list-isopropyl ether, ethylene glycol list-n-butyl ether, ethylene glycol list-tertiary butyl ether, Diethylene Glycol list-n-butyl ether, triethylene glycol butyl ether, Diethylene Glycol list-tertiary butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list-tertiary butyl ether, propylene glycol list-positive propyl ether, propylene glycol list-isopropyl ether, propylene glycol list-n-butyl ether, dipropylene glycol list-n-butyl ether, dipropylene glycol list-positive propyl ether, dipropylene glycol list-isopropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, diethylene glycol ethylmethyl ether, Diethylene Glycol methyl-n-butyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, dimethyl ether, dipropylene glycol diethyl ether, tripropylene glycol dme, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, 2-butanols, the trimethyl carbinol, isopropylcarbinol, Pentyl alcohol, 2-amylalcohol, 3-amylalcohol, and alcohols or the glycols such as tertiary amyl alcohol, DMF, N,N-dimethylacetamide, 2-Pyrrolidone, METHYLPYRROLIDONE, 2- oxazolidone, DMI, dimethyl sulfoxide (DMSO), tetramethylene sulfone and 1,1,3,3-tetramethyl-urea.

Solvent can be used alone a kind, also can combine two or more and use.The content of organic solvent is not particularly limited, and can suitably determine as required.Such as, when making the perviousness excellence of ink to printing medium, preferably use be selected from 1,2-hexylene glycol, triethylene glycol butyl ether and dipropylene glycol monopropyl ether more than one.

(pH adjusting agent)

The ink used in present embodiment can contain pH adjusting agent.PH adjusting agent can make the adjustment of the pH value of ink become easy.As pH adjusting agent, be not particularly limited, such as, mineral acid can be enumerated (such as, sulfuric acid, hydrochloric acid, nitric acid etc.), mineral alkali (such as, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia etc.), organic bases (trolamine, diethanolamine, monoethanolamine, tripropanol amine), organic acid (such as, hexanodioic acid, citric acid, succsinic acid etc.) etc.PH adjusting agent can be used alone a kind, also can mix two or more and use.

(other compositions)

The ink used in present embodiment, in order to maintain its storage stability and the ejection stability from shower nozzle well, in order to improve blocking or in order to prevent the deterioration of ink, dissolution aids, viscosity modifier, pH adjusting agent, antioxidant, sanitas, mould inhibitor, sanitas and for catching various additives such as the sequestrants of metal ion disperseing to impact suitably can be added.

[embodiment]

Below, embodiment and comparative example is used to be specifically described the present invention.The present invention is not by the following any restriction of embodiment.

[material of ink]

The main raw of the ink used in following embodiment and comparative example is as follows.

(with reference to table 8 ~ table 12)

(colorant)

Y-1: with reference to table 8

Y-2: with reference to table 8

Y-3: directly Huang 132

Y-4: acid yellow 23

M-1: with reference to table 9

M-2: with reference to table 9

M-3: reactive red 141

M-4: Acid Red 249

C-1: with reference to table 10

C-2: with reference to table 10

C-3: directly indigo plant 199

C-4: acid blue 9

Bk-1: with reference to table 11

Bw-1: with reference to table 11

Bk-2: directly black 195

Bk-3: with reference to table 12

Bk-4: with reference to table 12

Pig-Bk:CWE-50, material: carbon black (self-dispersion type)

(tensio-active agent)

SAA1:OLFINEEXP4300: the carbonatoms 12 of main chain, has the addition of oxyethane, 2,5,8,11-tetramethyl--6-dodecyne-5,8-diol ethoxylate (Nishin Chemical Industry Co. Lt)

SAA2:SurfynolDF110D: the carbonatoms 12 of main chain, without the addition of oxyethane, 2,5,8,11-tetramethyl--6-dodecyne-5,8-glycol (AirProducts Inc. trade(brand)name)

SAA3:Surfynol104PG50: the carbonatoms 10 of main chain, without the addition of oxyethane, 2,4,7,9-tetramethyl--5-decine-4,7-glycol (AirProducts Inc. trade(brand)name)

SAA4:OLFINEE1010: the carbonatoms 10 of main chain, the ethoxylate (Nishin Chemical Industry Co. Lt) of addition mole number 10,2,4,7,9-tetramethyl--5-decine-4, the 7-glycol of oxyethane

The ethoxylate (Nishin Chemical Industry Co. Lt) of SAA5:OLFINEE1004: the carbonatoms 10 of main chain, ethyleneoxide addition mole number 4,2,4,7,9-tetramethyl--5-decine-4,7-glycol

SAA6:OLFINE82W: the carbonatoms 8 of main chain, without the addition of oxyethane, 3,6-dimethyl-4-octyne-3,6-glycol (Nishin Chemical Industry Co. Lt)

(polyoxyalkylene alkyl)

POAAE1:NoigenDL-0415 (the first industrial pharmaceutical Inc.)

POAAE2:NoigenET-116B (the first industrial pharmaceutical Inc.)

POAAE3:NoigenET-106A (the first industrial pharmaceutical Inc.)

(solvent)

Triethylene glycol

Triethylene glycol butyl ether

Propylene glycol

Dipropylene glycol

Glycerine

(pH adjusting agent)

Trolamine

[preparation of ink]

Mix each material by the composition shown in following table 1 ~ 5, fully stir, obtain each ink.Specifically, each homogenize material is mixed, removes nonsoluble with strainer, prepare each ink thus.Should illustrate, in following table 1 ~ 5, the unit of numerical value is quality %, adds up to 100.0 quality %.

(manufacture of ink group)

By the combination shown in table 4 ~ 5, each ink obtained as described above carried out combining and make ink group.

[table 2]

Composition	Content
		Colorant	Table 1
Tensio-active agent	Table 3
		Polyoxyalkylene alkyl	Table 3
Triethylene glycol	10
		Triethylene glycol butyl ether	8
Propylene glycol	1
		Dipropylene glycol	1
Glycerine	10
		Trolamine	0.5
Water	Surplus
		Add up to	100

[table 3]

	Bk-04
		Bk-3	2.0
Bk-4	2.0
		Bw-1	1.0
Ozone resistance	○
		Solidity to corrosion	○
Colorrendering quality	○

(ozone resistance)

Use ink-jet printer EP-803 (Seiko Epson Corp's system), and use above-mentioned ink group, record thing is made by yellow, magenta, cyan and black (wherein, only containing black when ink group contains black ink composition) formation, the solid image that adjusts in the OD value of the respective color mode that is 0.9 ~ 1.1 in the upper printing of photo paper using < gloss > (Seiko Epson Corp's system).

Reflection of the concentration (trade(brand)name: Spectrolino, Gretag Inc.) is used to measure the OD value (D0) of the record thing obtained.Thereafter, use ozone ageing tester (trade(brand)name: OMS-L, Suga trier Co., Ltd. system) by record thing temperature be 23 DEG C, humidity be the condition of 50%RH, ozone concn 5ppm under expose 40 hours, 60 hours, 80 hours.After exposure, reflection of the concentration (trade(brand)name: Spectrolino, Gretag Inc.) is used to measure the OD value (D) of record thing, utilize following formula to obtain optical concentration survival rate (ROD), evaluate ozone resistance according to following determinating reference.

ROD(％)＝(D/D0)×100

Condition determination: gauge without light source strainer, light source: D50, field angle 2 degree

(metewand)

A: even if exposing 80 hours ROD is also more than 70%.

B: even if exposing 60 hours ROD is also more than 70%, if but expose 80 hours, ROD is less than 70%.

C: even if exposing 40 hours ROD is also more than 70%, if but expose 60 hours, ROD is less than 70%.

D: if expose 40 hours, ROD is less than 70%.

(color balance)

For the record thing after the exposure obtained by above-mentioned " evaluation of ozone resistance ", obtain the difference (ROD is poor) of the maxima and minima of the ROD of each color, evaluate color balance according to following determinating reference.

(metewand)

A: even if expose 80 hours ROD differences be also less than 15 points.

B: even if expose ROD difference for 60 hours be also less than 15 points, if but expose 80 hours, ROD difference is more than 15 points.

C: even if expose 40 hours ROD differences be also less than 15 points, if but expose 60 hours, ROD difference is more than 15 points.

D: if expose 40 hours, ROD difference is more than 15 points.

(wet fastness)

Use ink-jet printer EP-803 (Seiko Epson Corp's system), and use above-mentioned ink group, at photo paper using < gloss > (Seiko Epson Corp's system) upper process yellow, magenta, cyan and black (wherein, only contain black when ink group contains black ink composition) color word and hollow word (on the solid image of each color with hollow form formed word), at 24 DEG C, under 50%RH environment dry 24 hours, make record thing thus.

By the record thing that obtains 40 DEG C, leave standstill 7 days under the environment of 85%RH.By the word of visual observation record thing and the degree of oozing of spreading and sinking in of hollow word, according to following determinating reference, evaluate wet fastness.

(metewand)

A: can't see oozing out of colorant completely.

B: almost can't see oozing out of colorant.

C: see oozing out of colorant, civilian glyph is disintegrated.

D: see oozing out of colorant, word is thicker, hollow word entirety dyes the color of colorant.

(colorrendering quality)

Use ink-jet printer EP-803 (Seiko Epson Corp's system), also use above-mentioned ink group, photo paper setting, beauty, Bi-D, without under the pattern of color correction, photo paper using < gloss > (Seiko Epson Corp's system) prints look-up table, makes record thing thus.

The L* value, a* value, the b* value that obtain by measuring record thing, gamut volume when being all 1 by the L* value specified using CIE, a* value, b* value, as 1, calculates color reproduction range volume (gamut volume).In addition, similarly use ink group (benchmark ink group) disclosed in the embodiment 2 of Japanese Unexamined Patent Publication 2005-105135 publication to make record thing, calculate gamut volume.Calculate using the gamut volume of benchmark ink group as 100% time the gamut volume rate of above-mentioned ink group, according to following determinating reference evaluate color reproducibility.

(metewand)

A: gamut volume rate is more than 110%.

B: gamut volume rate is more than 105% and be less than 110%.

C: gamut volume rate is more than 100% and be less than 105%.

D: gamut volume rate is less than 100%.

(steady dissolution)

When preparing Yellow ink, magenta ink, cyan ink and black ink (wherein, only containing black ink when ink group contains black ink composition), mix each composition, stir 2 hours.Thereafter, to each ink, whether can uniform dissolution (dispersion) by visual observation material composition, according to following determinating reference, evaluate steady dissolution.

(metewand)

A: material composition uniform dissolution (dispersion), does not see and dissolves residual seston.

B: by room temperature carrying out the stirring of more than 1 hour, material composition uniform dissolution (dispersion), does not see and dissolves residual seston.

C: material composition does not dissolve (dispersion), dissolving is residual to be observed with the form of seston.

(initial fillibility)

Each ink group of preparation is filled in the ink tank of ink-jet printer (L800 (ProductName), Seiko Epson Corp's system).According to the initial to-fill procedure set by L800, carry out the initial filling action to shower nozzle.Afterwards, in order to confirm whether ink from whole nozzle ejections of shower nozzle, can implement nozzle check.When existence can not spray the nozzle of ink, carry out clean (attraction of the ink in nozzle) of shower nozzle, again implement nozzle check thereafter.Clean number of times required till can spraying from whole nozzle based on ink, by the following initial fillibility of metewand evaluation.Evaluation result is shown in following table 6 ~ 7.

(metewand)

A: only sprayed from whole nozzle by initial to-fill procedure.

B: required cleaning time be 1 time to ink can spray from whole nozzle.

C: required cleaning time be more than 2 times to ink can spray from whole nozzle.

(printing stability continuously)

According to above-mentioned " evaluation of initial fillibility ", confirm that ink can after whole nozzle ejections of shower nozzle, use common paper (the P paper (ProductName) of each ink composite and A4 size, FujiXerox Inc.), print the image of 70% rate of load condensate, carry out the evaluation of continuous printing stability thus.Printing number carries out the continuous printing 2 times of 500, adds up to 1000.Thereafter, implement nozzle check, based on the radical of drain spray mouth, evaluate continuous printing stability according to following metewand.Evaluation result is shown in following table 6 ~ 7.

(metewand)

A: the radical that drain spray mouth occurs is 1.

B: the radical that drain spray mouth occurs is less than 2.

C: the radical that drain spray mouth occurs is more than 3.

(bleed-resistant)

Use ink-jet printer EP-803 (Seiko Epson Corp's system), and use above-mentioned ink group, photo paper setting, beauty, Bi-D, without under the pattern of color correction, at the solid image that photo paper using < gloss > (Seiko Epson Corp's system) upper printing rate of load condensate is 80%, 90%, 100%, make record thing thus.

Row visual observation is infiltered to the spreading and sinking in of border of the color of the posting field of obtained record thing, according to following metewand, evaluates bleeding resistance.

(metewand)

A: rate of load condensate does not produce spreading and sinking between color for 100% time and oozes.

B: rate of load condensate does not produce spreading and sinking between color for 90% time and oozes.

C: rate of load condensate less than 80% does not produce spreading and sinking between color and oozes.

[table 8]

[table 9]

[table 10]

[table 11]

[table 12]

Bk-3：

Bk-4：

Claims

1. an ink group, at least possess Yellow ink, magenta ink and cyan ink, described Yellow ink contains more than a kind in the colorant being selected from and being represented by following formula (Y-1) and following formula (Y-2), described magenta ink contains more than a kind in the colorant being selected from and being represented by following formula (M-1) and following formula (M-2), described cyan ink contains more than a kind in the colorant being selected from and being represented by following formula (C-1) and following formula (C-2)

In formula (Y-1), R ₄represent substituting group, R ₅expression-OR ₆or-NHR ₇, R ₆and R ₇represent hydrogen atom or substituting group, X ₃represent the linking group of divalent, n0 is 0 or 1, Ar ₃represent the heterocyclic radical of divalent, Ar ₄represent alkyl, aryl or triazinyl,

In formula (Y-2), R ₁represent hydrogen atom or substituting group, R ₂represent substituting group, R ₃represent ionic hydrophilic radical or can form the alkyl of ring, n4 is 0 ~ 4, n5 is 2 ~ 5,

In formula (M-1), A ^m1the alkylidene group representing the alkylidene group of carbonatoms 1 or 2, the carbonatoms 1 or 2 containing phenylene or the group represented by following formula (M-1-1), X ^m1represent amino, hydroxyl, chlorine atom or the phenoxy group by sulfo group or carboxyl substituted,

In formula (M-1-1), R ^m1represent hydrogen atom or alkyl,

In described formula (M-2), A ^m2represent 5 yuan of heterocyclic radicals,

G ^m2, R ^m21, R ^m22represent hydrogen atom independently of one another, halogen atom, aliphatic group, aromatic group, heterocyclic radical, cyano group, carboxyl, formamyl, alkoxy carbonyl, aryloxycarbonyl, acyl group, hydroxyl, alkoxyl group, aryloxy, silyl oxygen base, acyloxy, carbamoyloxy, heterocyclic oxy group, alkoxyl group carbonyl oxygen base, aryloxy carbonyl oxygen base, by the amino that alkyl or aryl or heterocyclic radical replace, acyl amino, urea groups, sulphamoylamino, alkoxycarbonyl amino, aryloxycarbonylamino, alkyl and arlysulfonylamino, aryloxycarbonylamino, nitro, alkyl and artyl sulfo, alkyl and aryl sulfonyl, alkyl and aryl sulfonyl kia, sulfamyl, sulfo group or heterocyclethio, G ^m2, R ^m21, R ^m22can be substituted further,

R ^m21with R ^m23or R ^m23with R ^m24can bonding and form 5 ~ 6 rings,

In formula (C-1),

R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄and R ₁₅represent hydrogen atom independently of one another, halogen atom, alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl, heterocyclic radical, cyano group, hydroxyl, nitro, amino, alkylamino, alkoxyl group, aryloxy, amide group, arylamino, urea groups, sulphamoylamino, alkyl sulfenyl, artyl sulfo, alkoxycarbonyl amino, sulfoamido, formamyl, sulfamyl, alkoxy carbonyl, heterocyclic oxy group, azo-group, acyloxy, carbamoyloxy, silyl oxygen base, aryloxycarbonyl, aryloxycarbonylamino, imide, heterocyclethio, phosphoryl, acyl group or ionic hydrophilic radical, these groups can have substituting group further,

Z ₁, Z ₂, Z ₃and Z ₄independently of one another represent replace or without replace alkyl, replacement or without replace cycloalkyl, replacement or without replace thiazolinyl, replacement or without replace aralkyl, replacement or without replace aryl or replace or without replace heterocyclic radical, wherein, Z ₁, Z ₂, Z ₃and Z ₄in at least 1 there is ionic hydrophilic radical alternatively base,

L, m, n, p, q ₁, q ₂, q ₃and q ₄represent 1 or 2 independently of one another,

M ₁represent hydrogen atom, metallic element, metal oxide, metal hydroxides or metal halide,

In formula (C-2), R ₁, R ₄, R ₅, R ₈, R ₉, R ₁₂, R ₁₃and R ₁₆represent hydrogen atom independently of one another, halogen atom, alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl, heterocyclic radical, cyano group, hydroxyl, nitro, amino, alkylamino, alkoxyl group, aryloxy, amide group, arylamino, urea groups, sulphamoylamino, alkyl sulfenyl, artyl sulfo, alkoxycarbonyl amino, sulfoamido, formamyl, sulfamyl, alkoxy carbonyl, heterocyclic oxy group, azo-group, acyloxy, carbamoyloxy, silyl oxygen base, aryloxycarbonyl, aryloxycarbonylamino, imide, heterocyclethio, phosphoryl, acyl group or ionic hydrophilic radical, these groups can have substituting group further,

Z ₅, Z ₆, Z ₇and Z ₈independently of one another represent replace or without replace alkyl, replacement or without replace cycloalkyl, replacement or without replace thiazolinyl, replacement or without replace aralkyl, replacement or without replace aryl or replace or without replace heterocyclic radical, wherein, Z ₅, Z ₆, Z ₇and Z ₈in at least 1 there is ionic hydrophilic radical alternatively base,

T, u, v, w, q ₅, q ₆, q ₇and q ₈represent 1 or 2 independently of one another,

2. ink group according to claim 1, wherein, the carbonatoms that described Yellow ink, described magenta ink or described cyan ink contain main chain is the oxirane affixture of the alkyne diol of more than 12 and the carbonatoms of main chain is the alkyne diol of more than 10.

3. the ink group according to claims 1 or 2, wherein, described Yellow ink, described magenta ink or described cyan ink contain polyoxyalkylene alkyl.

4. the ink group according to any one of claims 1 to 3, wherein, the content of the carbonatoms of the main chain contained in described Yellow ink to be the content of the oxirane affixture of the alkyne diol of more than 12 than the carbonatoms of the main chain contained in described magenta ink or described cyan ink the be oxirane affixture of the alkyne diol of more than 12 is many.

5. the ink group according to any one of Claims 1 to 4, wherein, the carbonatoms of the main chain contained in described Yellow ink, described magenta ink or described cyan ink is the content of the oxirane affixture of the alkyne diol of more than 12 is 0.050 ~ 1.0 quality %.

6. the ink group according to any one of Claims 1 to 5, wherein, the content of the polyoxyalkylene alkyl contained in described Yellow ink, described magenta ink or described cyan ink is 0.10 ~ 0.30 quality %.

7. the ink group according to any one of claim 1 ~ 6, wherein, described magenta ink contains the colorant represented by described formula (M-1) and described formula (M-2).

8. the ink group according to any one of claim 1 ~ 7, wherein, described cyan ink contains the colorant represented by described formula (C-1) and described formula (C-2).

9. the ink group according to any one of claim 1 ~ 8, wherein, described Yellow ink contains the colorant represented by described formula (Y-1) and described formula (Y-2).

10. the ink group according to any one of claim 1 ~ 9, wherein, possesses at least one party in dyestuff black ink and Pigment black color ink further.

11. ink groups according to any one of claim 1 ~ 10, wherein, described dyestuff black ink contains at least a kind in the azo-compound or its salt that are selected from and are represented by following formula (Bk-1) and the colorant represented by following formula (Bw-1)

In formula (Bk-1), R ¹, R ², R ⁵, R ⁶and R ⁷represent hydrogen atom independently of one another; Halogen atom; Cyano group; Hydroxyl; Carboxyl; Sulfo group; Sulfamyl; N-alkyl amino sulfonyl; N-phenylaminosulfonyl group; The alkyl sulphonyl of the carbonatoms 1 ~ 4 that can be optionally substituted by a hydroxyl group; Phospho; Nitro; Acyl group; Urea groups; The alkyl of the carbonatoms 1 ~ 4 that can be replaced by the alkoxyl group of hydroxyl or carbonatoms 1 ~ 4; Alkyl can by the alkoxyl group of the carbonatoms 1 ~ 4 of the alkoxyl group of hydroxyl, carbonatoms 1 ~ 4, sulfo group or carboxyl substituted; Acyl amino; The phenyl sulfonyl amino that alkyl sulfonyl-amino or phenyl can be replaced by halogen atom, alkyl or nitro; R ³and R ⁴represent hydrogen atom independently of one another; Halogen atom; Cyano group; Carboxyl; Sulfo group; Nitro; The alkyl of the carbonatoms 1 ~ 4 that can be replaced by the alkoxyl group of hydroxyl or carbonatoms 1 ~ 4; Alkyl can by the alkoxyl group of the carbonatoms 1 ~ 4 of the alkoxyl group of hydroxyl, carbonatoms 1 ~ 4, sulfo group or carboxyl substituted; Acyl amino; The phenyl sulfonyl amino that alkyl sulfonyl-amino or phenyl can be replaced by halogen atom, alkyl or nitro; N represents 0 or 1;

In formula (Bw-1), R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷and R ²⁸represent hydrogen atom independently of one another; Halogen atom; Sulfo group; Carboxyl; Sulfamyl; Formamyl; The alkyl of carbonatoms 1 ~ 4; The alkoxyl group of carbonatoms 1 ~ 4; By the alkoxyl group being selected from the carbonatoms 1 ~ 4 that at least a kind of group in hydroxyl, the alkoxyl group of carbonatoms 1 ~ 4, the alkoxyl group of hydroxyl carbon atom number 1 ~ 4, sulfo group and carboxyl replaces of alternatively base; The alkyl-carbonyl-amino of carbonatoms 1 ~ 4; By the alkyl-carbonyl-amino of the carbonatoms 1 ~ 4 of carboxyl substituted; Urea groups; The alkyl urea groups of single carbon atom number 1 ~ 4; The alkyl urea groups of two carbonatomss 1 ~ 4; By the alkyl urea groups being selected from the single carbon atom number 1 ~ 4 that at least a kind of group in hydroxyl, sulfo group and carboxyl replaces of alternatively base; By the alkyl urea groups being selected from two carbonatomss 1 ~ 4 that at least a kind of group in hydroxyl, sulfo group and carboxyl replaces of alternatively base; Benzoyl-amido; Phenyl ring is selected from the benzoyl-amido that at least a kind of group in halogen atom, the alkyl of carbonatoms 1 ~ 4, nitro, sulfo group and carboxyl replaces; BENZENESUFONYLAMINO; Or phenyl ring is selected from the phenyl sulfonyl amino that at least a kind of group in halogen atom, the alkyl of carbonatoms 1 ~ 4, nitro, sulfo group and carboxyl replaces; X represents the crosslinked group of divalent.

12. according to the ink group in claim 1 ~ 10 described in wantonly 1, wherein, described dyestuff black ink contains at least a kind in the azo-compound or its salt that are selected from and are represented by following formula (Bk-3) and the colorant represented by following formula (Bk-4)

13. the ink group according to claim 10 or 11, wherein, described Pigment black color ink contains self-dispersing pigments.